Semiconductor device and manufacturing method thereof, module, and electronic device

ABSTRACT

A transistor with stable electrical characteristics or a transistor with normally-off electrical characteristics. The transistor is a semiconductor device including a conductor, a semiconductor, a first insulator, and a second insulator. The semiconductor is over the first insulator. The conductor is over the semiconductor. The second insulator is between the conductor and the semiconductor. The first insulator includes fluorine and hydrogen. The fluorine concentration of the first insulator is higher than the hydrogen concentration of the first insulator.

TECHNICAL FIELD

The present invention relates to, for example, a transistor or a semiconductor device. The present invention relates to, for example, a method for manufacturing a transistor or a semiconductor device. The present invention relates to, for example, a display device, a light-emitting device, a lighting device, a power storage device, a memory device, a processor, or an electronic device. The present invention relates to a method for manufacturing a display device, a liquid crystal display device, a light-emitting device, a memory device, or an electronic device. The present invention relates to a driving method of a display device, a liquid crystal display device, a light-emitting device, a memory device, or an electronic device.

Note that one embodiment of the present invention is not limited to the above technical field. The technical field of one embodiment of the invention disclosed in this specification and the like relates to an object, a method, or a manufacturing method. In addition, one embodiment of the present invention relates to a process, a machine, manufacture, or a composition of matter.

In this specification and the like, a semiconductor device generally means a device that can function by utilizing semiconductor characteristics. A display device, a light-emitting device, a lighting device, an electro-optical device, a semiconductor circuit, and an electronic device include a semiconductor device in some cases.

BACKGROUND ART

A technique for forming a transistor by using a semiconductor over a substrate having an insulating surface has attracted attention. The transistor is applied to a wide range of semiconductor devices such as an integrated circuit and a display device. Silicon is known as a semiconductor applicable to a transistor.

As silicon which is used as a semiconductor of a transistor, either amorphous silicon or polycrystalline silicon is used depending on the purpose. For example, in the case of a transistor included in a large display device, it is preferable to use amorphous silicon, which can be used to form a film on a large substrate with the established technique. In the case of a transistor included in a high-performance display device where a driver circuit and a pixel circuit are formed over the same substrate, it is preferable to use polycrystalline silicon, which can be used to form a transistor having a high field-effect mobility. As a method for forming polycrystalline silicon, high-temperature heat treatment or laser light treatment which is performed on amorphous silicon has been known.

In recent years, transistors including oxide semiconductors (typically, In—Ga—Zn oxide) have been actively developed.

Oxide semiconductors have been researched since early times. In 1988, there was a disclosure of a crystal In—Ga—Zn oxide that can be used for a semiconductor element (see Patent Document 1). In 1995, a transistor including an oxide semiconductor was invented, and its electrical characteristics were disclosed (see Patent Document 2).

The transistor including an oxide semiconductor has different features from a transistor including amorphous silicon or polycrystalline silicon. For example, a display device in which a transistor including an oxide semiconductor is used is known to have small power consumption. An oxide semiconductor can be formed by a sputtering method or the like, and thus can be used in a transistor included in a large display device. Because a transistor including an oxide semiconductor has high field-effect mobility, a high-performance display device in which, for example, a driver circuit and a pixel circuit are formed over the same substrate can be obtained. In addition, there is an advantage that capital investment can be reduced because part of production equipment for a transistor including amorphous silicon can be retrofitted and utilized.

For mass production of semiconductor devices such as display devices, stable electrical characteristics of transistors including an oxide semiconductor are required. For example, hydrogen that enters an oxide semiconductor is a factor of change in electrical characteristics of a transistor. Patent Document 3 discloses that hydrogen in an oxide semiconductor is trapped by an insulator including halogen.

REFERENCE Patent Document

[Patent Document 1] Japanese Published Patent Application No. S63-239117

[Patent Document 2] Japanese translation of PCT international application No. H11-505377

[Patent Document 3] Japanese Published Patent Application No. 2011-109078

DISCLOSURE OF INVENTION

An object is to provide a transistor with stable electrical characteristics. Another object is to provide a transistor with normally-off electrical characteristics. Another object is to provide a transistor with a small subthreshold swing value. Another object is to provide a transistor having a small short-channel effect. Another object is to provide a transistor having a low leakage current in an off state. Another object is to provide a transistor with excellent electrical characteristics. Another object is to provide a highly reliable transistor. Another object is to provide a transistor with high frequency characteristics.

Another object is to provide a semiconductor device including the transistor. Another object is to provide a module including the semiconductor device. Another object is to provide an electronic device including the semiconductor device or the module. Another object is to provide a novel semiconductor device. Another object is to provide a novel module. Another object is to provide a novel electronic device.

Note that the descriptions of these objects do not disturb the existence of other objects. In one embodiment of the present invention, there is no need to achieve all the objects. Other objects will be apparent from and can be derived from the description of the specification, the drawings, the claims, and the like.

(1) One embodiment of the present invention is a semiconductor device including a conductor, a semiconductor, a first insulator, and a second insulator. The semiconductor is over the first insulator. The conductor is over the semiconductor. The second insulator is between the conductor and the semiconductor. The first insulator includes fluorine and hydrogen. The fluorine concentration of the first insulator is higher than the hydrogen concentration of the first insulator.

(2) One embodiment of the present invention is a semiconductor device including a conductor, a semiconductor, a first insulator, and a second insulator. The semiconductor is over the conductor. The first insulator is between the conductor and the semiconductor. The second insulator is over the semiconductor. The second insulator includes fluorine and hydrogen. The fluorine concentration of the second insulator is higher than the hydrogen concentration of the second insulator.

(3) One embodiment of the present invention is a semiconductor device including a conductor, a semiconductor, a first insulator, and a second insulator. The semiconductor is over the first insulator. The conductor is over the semiconductor. The second insulator is between the conductor and the semiconductor. The second insulator includes fluorine and hydrogen. The fluorine concentration of the second insulator is higher than the hydrogen concentration of the second insulator.

(4) One embodiment of the present invention is a semiconductor device including a conductor, a semiconductor, a first insulator, and a second insulator. The semiconductor is over the conductor. The first insulator is between the conductor and the semiconductor. The second insulator is over the semiconductor. The first insulator includes fluorine and hydrogen. The fluorine concentration of the first insulator is higher than the hydrogen concentration of the first insulator.

(5) One embodiment of the present invention is the semiconductor device according to any one of (1) to (4), in which the first insulator includes oxygen and silicon.

(6) One embodiment of the present invention is the semiconductor device according to any one of (1) to (5), in which the second insulator includes oxygen and silicon.

(7) One embodiment of the present invention is the semiconductor device according to any one of (1) to (6), in which the semiconductor includes a first semiconductor and a second semiconductor, and the second semiconductor has a larger electron affinity than the first semiconductor.

(8) One embodiment of the present invention is the semiconductor device according to any one of (1) to (6), in which the semiconductor includes a first semiconductor and a second semiconductor, and the second semiconductor has a larger energy gap than the first semiconductor.

(9) One embodiment of the present invention is the semiconductor device according to any one of (1) to (6), in which the semiconductor includes indium, an element M (aluminum, gallium, yttrium, or tin), zinc, and oxygen.

(10) One embodiment of the present invention is a module including the semiconductor device according to any one of (1) to (9) and a printed board.

(11) One embodiment of the present invention is an electronic device including the semiconductor device according to any one of (1) to (9) or the module according to (10), and at least one of a speaker, an operation key, and a battery.

(12) One embodiment of the present invention is a method of manufacturing a semiconductor device, including the steps of forming a conductor; forming a first insulator over the conductor; forming a semiconductor over the conductor with the first insulator positioned therebetween; forming a second insulator over the semiconductor; forming a third insulator over the second insulator; and adding fluorine to the second insulator through the third insulator.

(13) One embodiment of the present invention is the method of manufacturing a semiconductor device, according to (12), in which the second insulator includes oxygen and silicon.

(14) One embodiment of the present invention is the method of manufacturing a semiconductor device, according to (12) or (13), in which the third insulator includes nitrogen and silicon.

(15) One embodiment of the present invention is a method of manufacturing a semiconductor device, including the steps of: forming a semiconductor; forming a first insulator over the semiconductor; forming a second insulator over the first insulator; adding fluorine to the first insulator through the second insulator; and forming a conductor over the semiconductor with the first insulator and the second insulator positioned therebetween.

(16) One embodiment of the present invention is a method of manufacturing a semiconductor device, including the steps of: forming a first insulator; forming a second insulator over the first insulator; adding fluorine to the first insulator through the second insulator; forming a semiconductor; forming a third insulator over the semiconductor; and forming a conductor over the semiconductor with the third insulator positioned therebetween.

(17) One embodiment of the present invention is a method of manufacturing a semiconductor device, including the steps of: forming a first conductor; forming a first insulator over the first conductor; forming a second insulator over the first insulator; adding fluorine to the first insulator through the second insulator; forming a semiconductor over the first conductor with the first insulator and the second insulator positioned therebetween; forming a third insulator over the semiconductor; forming a fourth insulator over the third insulator; adding fluorine to the third insulator through the fourth insulator; and forming a second conductor over the semiconductor with the third insulator and the fourth insulator positioned therebetween.

(18) One embodiment of the present invention is the method of manufacturing a semiconductor device, according to any one of claims (12) to (17), in which the semiconductor includes a first semiconductor and a second semiconductor, and the second semiconductor has a larger electron affinity than the first semiconductor.

(19) One embodiment of the present invention is the method of manufacturing a semiconductor device, according to any one of claims (12) to (17), in which the semiconductor includes a first semiconductor and a second semiconductor, and the second semiconductor has a larger energy gap than the first semiconductor.

(20) One embodiment of the present invention is the method of manufacturing a semiconductor device, according to any one of claims (12) to (17), in which the semiconductor includes indium, an element M (aluminum, gallium, yttrium, or tin), zinc, and oxygen.

A transistor with stable electrical characteristics can be provided. A transistor with normally-off electrical characteristics can be provided. A transistor with a small subthreshold swing value can be provided. A transistor having a small short-channel effect can be provided. A transistor having a low leakage current in an off state can be provided. A transistor with excellent electrical characteristics can be provided. A highly reliable transistor can be provided. A transistor with high frequency characteristics can be provided.

A semiconductor device including the transistor can be provided. A module including the semiconductor device can be provided. An electronic device including the semiconductor device or the module can be provided. A novel semiconductor device can be provided. A novel module can be provided. A novel electronic device can be provided.

Note that the description of these effects does not disturb the existence of other effects. One embodiment of the present invention does not necessarily achieve all the effects listed above. Other effects will be apparent from and can be derived from the description of the specification, the drawings, the claims, and the like.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1A to 1C illustrate bonding states of a silicon oxide.

FIGS. 2A and 2B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 3A and 3B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 4A and 4B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 5A and 5B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 6A and 6B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 7A to 7C are cross-sectional views each illustrating a transistor of one embodiment of the present invention.

FIGS. 8A to 8C are cross-sectional views each illustrating a transistor of one embodiment of the present invention.

FIG. 9 is a band diagram showing one embodiment of the present invention.

FIGS. 10A and 10B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 11A and 11B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 12A and 12B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 13A and 13B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 14A and 14B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 15A to 15C are cross-sectional views each illustrating a transistor of one embodiment of the present invention.

FIGS. 16A to 16C are cross-sectional views each illustrating a transistor of one embodiment of the present invention.

FIGS. 17A and 17B are band diagrams each showing one embodiment of the present invention.

FIGS. 18A and 18B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 19A and 19B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 20A and 20B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 21A and 21B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 22A and 22B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 23A and 23B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 24A and 24B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 25A to 25C are cross-sectional views each illustrating a transistor of one embodiment of the present invention.

FIGS. 26A to 26C are cross-sectional views each illustrating a transistor of one embodiment of the present invention.

FIGS. 27A and 27B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 28A and 28B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 29A and 29B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 30A and 30B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 31A and 31B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 32A and 32B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 33A and 33B are a top view and a cross-sectional view illustrating a method for manufacturing a transistor of one embodiment of the present invention.

FIGS. 34A to 34C are cross-sectional views each illustrating a transistor of one embodiment of the present invention.

FIGS. 35A to 35C are cross-sectional views each illustrating a transistor of one embodiment of the present invention.

FIGS. 36A and 36B are circuit diagrams each illustrating a semiconductor device of one embodiment of the present invention.

FIG. 37 is a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

FIG. 38 is a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

FIG. 39 is a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

FIG. 40 is a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

FIG. 41 is a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

FIG. 42 is a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

FIGS. 43A and 43B are circuit diagrams each illustrating a memory device of one embodiment of the present invention.

FIG. 44 is a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

FIG. 45 is a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

FIG. 46 is a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

FIG. 47 is a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

FIG. 48 is a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

FIG. 49 is a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

FIGS. 50A and 50B are top views each illustrating a semiconductor device of one embodiment of the present invention.

FIGS. 51A and 51B are block diagrams illustrating a semiconductor device of one embodiment of the present invention.

FIGS. 52A and 52B are cross-sectional views each illustrating a semiconductor device of one embodiment of the present invention.

FIGS. 53A and 53B are cross-sectional views each illustrating a semiconductor device of one embodiment of the present invention.

FIGS. 54A1 to 54A3 and 54B1 to 54B3 are perspective views and cross-sectional views of semiconductor devices of embodiments of the present invention.

FIG. 55 is a block diagram illustrating a semiconductor device of one embodiment of the present invention.

FIG. 56 is a circuit diagram illustrating a semiconductor device of one embodiment of the present invention.

FIGS. 57A to 57C are a circuit diagram, a top view, and a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

FIGS. 58A and 58B are a circuit diagram and a cross-sectional view illustrating a semiconductor device of one embodiment of the present invention.

FIGS. 59A to 59F are perspective views each illustrating an electronic device of one embodiment of the present invention.

FIGS. 60A to 60C are Cs-corrected high-resolution TEM images of a cross section of a CAAC-OS and FIG. 60D is a schematic cross-sectional view of the CAAC-OS.

FIGS. 61A to 61D are Cs-corrected high-resolution TEM images of a plane of a CAAC-OS.

FIGS. 62A to 62C show structural analysis of a CAAC-OS and a single crystal oxide semiconductor by XRD.

FIGS. 63A and 63B show electron diffraction patterns of a CAAC-OS.

FIG. 64 shows a change of crystal parts of an In—Ga—Zn oxide owing to electron irradiation.

FIGS. 65A and 65B are schematic views showing deposition models of a CAAC-OS and an nc-OS.

FIGS. 66A to 66C show an InGaZnO₄ crystal and a pellet.

FIGS. 67A to 67D are schematic views showing a deposition model of a CAAC-OS.

FIGS. 68A to 68C are graphs each explaining heat treatment.

FIG. 69 is a graph showing the amount of added fluorine in the depth direction.

FIG. 70 is a graph showing fluorine concentrations of samples in the depth direction.

FIG. 71 is a graph showing released gases from samples.

FIGS. 72A and 72B are graphs showing the results of measurement of unpaired electrons by ESR.

FIGS. 73A and 73B are cross-sectional STEM images of samples.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments and examples of the present invention will be described in detail with the reference to the drawings. However, the present invention is not limited to the description below, and it is easily understood by those skilled in the art that modes and details disclosed herein can be modified in various ways. Further, the present invention is not construed as being limited to description of the embodiments and the examples. In describing structures of the present invention with reference to the drawings, common reference numerals are used for the same portions in different drawings. Note that the same hatched pattern is applied to similar parts, and the similar parts are not especially denoted by reference numerals in some cases.

Note that the size, the thickness of films (layers), or regions in drawings is sometimes exaggerated for simplicity.

In this specification, the terms “film” and “layer” can be interchanged with each other.

A voltage usually refers to a potential difference between a given potential and a reference potential (e.g., a source potential or a ground potential (GND)). A voltage can be referred to as a potential and vice versa. Note that in general, a potential (a voltage) is relative and is determined depending on the amount relative to a certain potential. Therefore, a potential that is represented as a “ground potential” or the like is not always 0 V. For example, the lowest potential in a circuit may be represented as a “ground potential”. Alternatively, a substantially intermediate potential in a circuit may be represented as a “ground potential”. In these cases, a positive potential and a negative potential are set using the potential as a reference.

Note that the ordinal numbers such as “first” and “second” are used for convenience and do not denote the order of steps or the stacking order of layers. Therefore, for example, the term “first” can be replaced with the term “second”, “third”, or the like as appropriate. In addition, the ordinal numbers in this specification and the like do not correspond to the ordinal numbers which specify one embodiment of the present invention in some cases.

Note that a “semiconductor” has characteristics of an “insulator” in some cases when the conductivity is sufficiently low, for example. Further, a “semiconductor” and an “insulator” cannot be strictly distinguished from each other in some cases because a border therebetween is not clear. Accordingly, a “semiconductor” in this specification can be called an “insulator” in some cases. Similarly, an “insulator” in this specification can be called a “semiconductor” in some cases.

Further, a “semiconductor” has characteristics of a “conductor” in some cases when the conductivity is sufficiently high, for example. Further, a “semiconductor” and a “conductor” cannot be strictly distinguished from each other in some cases because a border therebetween is not clear. Accordingly, a “semiconductor” in this specification can be called a “conductor” in some cases. Similarly, a “conductor” in this specification can be called a “semiconductor” in some cases.

Note that impurities in a semiconductor refer to, for example, elements other than the main components of the semiconductor. For example, an element with a concentration of lower than 0.1 atomic % is an impurity. When an impurity is contained, the density of states (DOS) may be formed in a semiconductor, the carrier mobility may be decreased, or the crystallinity may be decreased. In the case where the semiconductor is an oxide semiconductor, examples of an impurity which changes characteristics of the semiconductor include Group 1 elements, Group 2 elements, Group 14 elements, Group 15 elements, and transition metals other than the main components; specifically, there are hydrogen (included in water), lithium, sodium, silicon, boron, phosphorus, carbon, and nitrogen, for example. In the case of an oxide semiconductor, oxygen vacancies may be formed by entry of impurities such as hydrogen. In the case where the semiconductor is silicon, examples of an impurity which changes characteristics of the semiconductor include oxygen, Group 1 elements except hydrogen, Group 2 elements, Group 13 elements, and Group 15 elements.

In this specification, the phrase “A has a region with a concentration B” includes, for example, “the concentration of the entire region in a region of A in the depth direction is B”, “the average concentration in a region of A in the depth direction is B”, “the median value of a concentration in a region of A in the depth direction is B”, “the maximum value of a concentration in a region of A in the depth direction is B”, “the minimum value of a concentration in a region of A in the depth direction is B”, “a convergence value of a concentration in a region of A in the depth direction is B”, and “a concentration in a region of A in which a probable value is obtained in measurement is B”.

In this specification, the phrase “A has a region with a size B, a length B, a thickness B, a width B, or a distance B” includes, for example, “the size, the length, the thickness, the width, or the distance of the entire region in a region of A is B”, “the average value of the size, the length, the thickness, the width, or the distance of a region of A is B”, “the median value of the size, the length, the thickness, the width, or the distance of a region of A is B”, “the maximum value of the size, the length, the thickness, the width, or the distance of a region of A is B”, “the minimum value of the size, the length, the thickness, the width, or the distance of a region of A is B”, “a convergence value of the size, the length, the thickness, the width, or the distance of a region of A is B”, and “the size, the length, the thickness, the width, or the distance of a region of A in which a probable value is obtained in measurement is B”.

Note that the channel length refers to, for example, the distance between a source (a source region or a source electrode) and a drain (a drain region or a drain electrode) in a region where a semiconductor (or a portion where a current flows in a semiconductor when a transistor is on) and a gate electrode overlap with each other or a region where a channel is formed in a plan view of the transistor. In one transistor, channel lengths in all regions are not necessarily the same. In other words, the channel length of one transistor is not limited to one value in some cases. Therefore, in this specification, the channel length is any one of values, the maximum value, the minimum value, or the average value in a region where a channel is formed.

The channel width refers to, for example, the length of a portion where a source and a drain face each other in a region where a semiconductor (or a portion where a current flows in a semiconductor when a transistor is on) and a gate electrode overlap with each other, or a region where a channel is formed. In one transistor, channel widths in all regions are not necessarily the same. In other words, the channel width of one transistor is not limited to one value in some cases. Therefore, in this specification, the channel width is any one of values, the maximum value, the minimum value, or the average value in a region where a channel is formed.

Note that depending on transistor structures, a channel width in a region where a channel is formed actually (hereinafter referred to as an effective channel width) is different from a channel width shown in a plan view of a transistor (hereinafter referred to as an apparent channel width) in some cases. For example, in a transistor having a three-dimensional structure, an effective channel width is greater than an apparent channel width shown in a plan view of the transistor, and its influence cannot be ignored in some cases. For example, in a miniaturized transistor having a three-dimensional structure, the proportion of a channel region formed in a side surface of a semiconductor is high in some cases. In that case, an effective channel width obtained when a channel is actually formed is greater than an apparent channel width shown in the plan view.

In a transistor having a three-dimensional structure, an effective channel width is difficult to measure in some cases. For example, to estimate an effective channel width from a design value, it is necessary to assume that the shape of a semiconductor is known as an assumption condition. Therefore, in the case where the shape of a semiconductor is not known accurately, it is difficult to measure an effective channel width accurately.

Therefore, in this specification, in a plan view of a transistor, an apparent channel width that is a length of a portion where a source and a drain face each other in a region where a semiconductor and a gate electrode overlap with each other is referred to as a surrounded channel width (SCW) in some cases. Further, in this specification, in the case where the term “channel width” is simply used, it may denote a surrounded channel width and an apparent channel width. Alternatively, in this specification, in the case where the term “channel width” is simply used, it may denote an effective channel width in some cases. Note that the values of a channel length, a channel width, an effective channel width, an apparent channel width, a surrounded channel width, and the like can be determined by obtaining and analyzing a cross-sectional TEM image and the like.

Note that in the case where electric field mobility, a current value per channel width, and the like of a transistor are obtained by calculation, a surrounded channel width may be used for the calculation. In that case, the values might be different from those calculated by using an effective channel width.

Note that in this specification, the description “A has a shape such that an end portion extends beyond an end portion of B” may indicate, for example, the case where at least one of end portions of A is positioned on an outer side than at least one of end portions of B in a top view or a cross-sectional view. Thus, the description “A has a shape such that an end portion extends beyond an end portion of B” can be read as the description “one end portion of A is positioned on an outer side than one end portion of B in a top view,” for example.

In this specification, the term “parallel” indicates that the angle formed between two straight lines is greater than or equal to −10° and less than or equal to 10°, and accordingly also includes the case where the angle is greater than or equal to −5° and less than or equal to 5°. A term “substantially parallel” indicates that the angle formed between two straight lines is greater than or equal to −30° and less than or equal to 30°. The term “perpendicular” indicates that the angle formed between two straight lines is greater than or equal to 80° and less than or equal to 100°, and accordingly also includes the case where the angle is greater than or equal to 85° and less than or equal to 95°. A term “substantially perpendicular” indicates that the angle formed between two straight lines is greater than or equal to 60° and less than or equal to 120°.

In this specification, trigonal and rhombohedral crystal systems are included in a hexagonal crystal system.

In this specification, a term “semiconductor” can be referred to as an “oxide semiconductor”. As the semiconductor, a Group 14 semiconductor such as silicon or germanium; a compound semiconductor such as silicon carbide, germanium silicide, gallium arsenide, indium phosphide, zinc selenide, or cadmium sulfide; or an organic semiconductor can be used.

<Transistor 1>

A transistor of one embodiment of the present invention is described below.

FIG. 2A, FIG. 3A, FIG. 4A, FIG. 5A, and FIG. 6A are top views illustrating a method for manufacturing a transistor. FIG. 2B, FIG. 3B, FIG. 4B, FIG. 5B, and FIG. 6B are each a cross-sectional view taken along dashed dotted lines A1-A2 and A3-A4 shown in the corresponding top view.

First, a substrate 400 is prepared.

As the substrate 400, an insulator substrate, a semiconductor substrate, or a conductor substrate may be used, for example. As the insulator substrate, a glass substrate, a quartz substrate, a sapphire substrate, a stabilized zirconia substrate (e.g., an yttria-stabilized zirconia substrate), or a resin substrate is used, for example. As the semiconductor substrate, a single material semiconductor substrate of silicon, germanium, or the like or a compound semiconductor substrate of silicon carbide, silicon germanium, gallium arsenide, indium phosphide, zinc oxide, gallium oxide, or the like is used, for example. A semiconductor substrate in which an insulator region is provided in the above semiconductor substrate, e.g., a silicon on insulator (SOI) substrate or the like is used. As the conductor substrate, a graphite substrate, a metal substrate, an alloy substrate, a conductive resin substrate, or the like is used. A substrate including a metal nitride, a substrate including a metal oxide, or the like is used. An insulator substrate provided with a conductor or a semiconductor, a semiconductor substrate provided with a conductor or an insulator, a conductor substrate provided with a semiconductor or an insulator, or the like is used. Alternatively, any of these substrates over which an element is provided may be used. As the element provided over the substrate, a capacitor, a resistor, a switching element, a light-emitting element, a memory element, or the like is used.

Alternatively, a flexible substrate may be used as the substrate 400. As a method for providing the transistor over a flexible substrate, there is a method in which the transistor is formed over a non-flexible substrate and then the transistor is separated and transferred to the substrate 400 which is a flexible substrate. In that case, a separation layer is preferably provided between the non-flexible substrate and the transistor. As the substrate 400, a sheet containing a fiber, a film, or a foil may be used. The substrate 400 may have elasticity. The substrate 400 may have a property of returning to its original shape when bending or pulling is stopped. Alternatively, the substrate 400 may have a property of not returning to its original shape. The thickness of the substrate 400 is, for example, greater than or equal to 5 μm and less than or equal to 700 μm, preferably greater than or equal to 10 μm and less than or equal to 500 μm, or further preferably greater than or equal to 15 μm and less than or equal to 300 μm. When the substrate 400 has a small thickness, the weight of the semiconductor device can be reduced. When the substrate 400 has a small thickness, even in the case of using glass or the like, the substrate 400 may have elasticity or a property of returning to its original shape when bending or pulling is stopped. Therefore, an impact applied to the semiconductor device over the substrate 400, which is caused by dropping or the like, can be reduced. That is, a durable semiconductor device can be provided.

For the substrate 400 which is a flexible substrate, metal, an alloy, resin, glass, or fiber thereof can be used, for example. The flexible substrate 400 preferably has a lower coefficient of linear expansion because deformation due to an environment is suppressed. The flexible substrate 400 is formed using, for example, a material whose coefficient of linear expansion is lower than or equal to 1×10⁻³/K, lower than or equal to 5×10⁻⁵/K, or lower than or equal to 1×10⁻⁵/K. Examples of the resin include polyester, polyolefin, polyamide (e.g., nylon or aramid), polyimide, polycarbonate, and acrylic. In particular, aramid is preferably used for the flexible substrate 400 because of its low coefficient of linear expansion.

Next, a conductor is formed. The conductor may be formed by a sputtering method, a chemical vapor deposition (CVD) method, a molecular beam epitaxy (MBE) method, a pulsed laser deposition (PLD) method, an atomic layer deposition (ALD) method, or the like.

CVD methods can be classified into a plasma enhanced CVD (PECVD) method using plasma, a thermal CVD (TCVD) method using heat, a photo CVD method using light, and the like. Moreover, the CVD method can include a metal CVD (MCVD) method and a metal organic CVD (MOCVD) method depending on a source gas.

In the case of a PECVD method, a high quality film can be obtained at relatively low temperature. Furthermore, a TCVD method does not use plasma and thus causes less plasma damage to an object. For example, a wiring, an electrode, an element (e.g., transistor or capacitor), or the like included in a semiconductor device might be charged up by receiving charges from plasma. In that case, accumulated charges might break the wiring, electrode, element, or the like included in the semiconductor device. Such plasma damage is not caused in the case of using a TCVD method, and thus the yield of a semiconductor device can be increased. In addition, since plasma damage does not occur in the deposition by a TCVD method, a film with few defects can be obtained.

An ALD method also causes less plasma damage to an object. An ALD method does not cause plasma damage during deposition, so that a film with few defects can be obtained.

Unlike in a deposition method in which particles ejected from a target or the like are deposited, in a CVD method and an ALD method, a film is formed by reaction at a surface of an object. Thus, a CVD method and an ALD method enable favorable step coverage almost regardless of the shape of an object. In particular, an ALD method enables excellent step coverage and excellent thickness uniformity and can be favorably used for covering a surface of an opening portion with a high aspect ratio, for example. On the other hand, an ALD method has a relatively low deposition rate; thus, it is sometimes preferable to combine an ALD method with another deposition method with a high deposition rate such as a CVD method.

When a CVD method or an ALD method is used, composition of a film to be formed can be controlled with a flow rate ratio of the source gases. For example, by the CVD method or the ALD method, a film with a desired composition can be formed by adjusting the flow ratio of a source gas. Moreover, with a CVD method or an ALD method, by changing the flow rate ratio of the source gases while forming the film, a film whose composition is continuously changed can be formed. In the case where the film is formed while changing the flow rate ratio of the source gases, as compared to the case where the film is formed using a plurality of deposition chambers, time taken for the deposition can be reduced because time taken for transfer and pressure adjustment is omitted. Thus, semiconductor devices can be manufactured with improved productivity.

Next, a resist or the like is formed over the conductor and processing is performed using the resist, whereby a conductor 413 is formed. Note that the case where the resist is simply formed also includes the case where a BARC is formed below the resist.

The resist is removed after the object is processed by etching or the like. For the removal of the resist, plasma treatment and/or wet etching are/is used. Note that as the plasma treatment, plasma ashing is preferable. In the case where the removal of the resist or the like is not enough, the remaining resist or the like may be removed using ozone water and/or hydrofluoric acid at a concentration higher than or equal to 0.001 volume % and lower than or equal to 1 volume %, and the like.

The conductor to be the conductor 413 may be formed to have a single-layer structure or a stacked-layer structure using a conductor containing, for example, one or more of boron, nitrogen, oxygen, fluorine, silicon, phosphorus, aluminum, titanium, chromium, manganese, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, molybdenum, ruthenium, silver, indium, tin, tantalum, and tungsten. An alloy or a compound of the above element may be used, for example, and a conductor containing aluminum, a conductor containing copper and titanium, a conductor containing copper and manganese, a conductor containing indium, tin, and oxygen, a conductor containing titanium and nitrogen, or the like may be used.

Then, an insulator 402 is formed (see FIGS. 2A and 2B). The insulator 402 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

The insulator 402 may be formed to have a single-layer structure or a stacked-layer structure including an insulator containing, for example, boron, carbon, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon, phosphorus, chlorine, argon, gallium, germanium, yttrium, zirconium, lanthanum, neodymium, hafnium, or tantalum.

The insulator 402 may be formed using aluminum oxide, magnesium oxide, silicon oxide, silicon oxynitride, silicon nitride oxide, silicon nitride, gallium oxide, germanium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, or tantalum oxide.

The insulator 402 preferably includes excess oxygen and/or a hydrogen trap.

Here, an insulator including excess oxygen may release oxygen, the amount of which is higher than or equal to 1×10¹⁸ atoms/cm³, higher than or equal to 1×10¹⁹ atoms/cm³, or higher than or equal to 1×10²⁰ atoms/cm³ (converted into the number of oxygen atoms) in thermal desorption spectroscopy (TDS) analysis in the range of a surface temperature of 100° C. to 700° C. or 100° C. to 500° C.

The method of measuring the amount of released oxygen using TDS analysis is described below.

The total amount of released gas from a measurement sample in TDS analysis is proportional to the integral value of the ion intensity of the released gas. Then, comparison with a reference sample is made, whereby the total amount of released gas can be calculated.

For example, the number of released oxygen molecules (N_(O2)) from a measurement sample can be calculated according to the following formula using the TDS results of a silicon substrate containing hydrogen at a predetermined density, which is a reference sample, and the TDS results of the measurement sample. Here, all gases having a mass-to-charge ratio of 32 which are obtained in the TDS analysis are assumed to originate from an oxygen molecule. Note that CH₃OH, which is a gas having the mass-to-charge ratio of 32, is not taken into consideration because it is unlikely to be present. Furthermore, an oxygen molecule including an oxygen atom having a mass number of 17 or 18 which is an isotope of an oxygen atom is also not taken into consideration because the proportion of such a molecule in the natural world is minimal

N_(O2)=N_(H2)/S_(H2)×S_(O2)×α

The value N_(H2) is obtained by conversion of the number of hydrogen molecules desorbed from the reference sample into densities. The value S_(H2) is the integral value of ion intensity in the case where the reference sample is subjected to the TDS analysis. Here, the reference value of the reference sample is set to N_(H2)/S_(H2). The value S_(O2) is the integral value of ion intensity when the measurement sample is analyzed by TDS. The value α is a coefficient affecting the ion intensity in the TDS analysis. Refer to Japanese Published Patent Application No. H6-275697 for details of the above formula. The amount of released oxygen was measured with a thermal desorption spectroscopy apparatus produced by ESCO Ltd., EMD-WA1000S/W using a silicon substrate containing a certain amount of hydrogen atoms as the reference sample.

Furthermore, in the TDS analysis, oxygen is partly detected as an oxygen atom. The ratio between oxygen molecules and oxygen atoms can be calculated from the ionization rate of the oxygen molecules. Note that, since the above α includes the ionization rate of the oxygen molecules, the number of the released oxygen atoms can also be estimated through the evaluation of the number of the released oxygen molecules.

Note that N_(O2) is the number of the released oxygen molecules. The number of released oxygen in the case of being converted into oxygen atoms is twice the number of the released oxygen molecules.

Furthermore, the insulator from which oxygen is released by heat treatment may contain a peroxide radical. Specifically, the spin density of a signal attributed to the peroxide radical is greater than or equal to 5×10¹⁷ spins/cm³. Note that the insulator containing a peroxide radical may have an asymmetric signal with a g factor of approximately 2.01 in electron spin resonance (ESR).

The insulator 402 may have a function of preventing diffusion of impurities from the substrate 400.

Next, fluorine ions may be added to the insulator 402 so that the insulator 402 includes excess oxygen and a hydrogen trap. The reason why excess oxygen and a hydrogen trap are formed by addition of fluorine ions will be described later. The addition of fluorine ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 2 kV and less than or equal to 100 kV, preferably greater than or equal to 5 kV and less than or equal to 50 kV at a dose of greater than or equal to 1×10¹⁴ ions/cm² and less than or equal to 5×10¹⁶ ions/cm², preferably greater than or equal to 5×10¹⁴ ions/cm² and less than or equal to 1×10¹⁶ ions/cm², for example.

Next, a semiconductor to be the semiconductor 406 a is formed. The semiconductor to be the semiconductor 406 a can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, oxygen ions may be added so that a semiconductor to be the semiconductor 406 a includes excess oxygen. The addition of oxygen ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 2 kV and less than or equal to 10 kV at a dose of greater than or equal to 5×10¹⁴ ions/cm′ and less than or equal to 5×10¹⁶ ions/cm², for example.

Next, fluorine ions may be added to the insulator 402 so that the insulator 402 includes excess oxygen and a hydrogen trap. The addition of fluorine ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 5 kV and less than or equal to 200 kV, preferably greater than or equal to 20 kV and less than or equal to 100 kV at a dose of greater than or equal to 1×10¹⁴ ions/cm² and less than or equal to 5×10¹⁶ ions/cm², preferably greater than or equal to 5×10¹⁴ ions/cm² and less than or equal to 1×10¹⁶ ions/cm², for example. Note that the addition of oxygen ions to the semiconductor to be the semiconductor 406 a and the addition of fluorine ions to the insulator 402 may be performed in reverse order.

Next, a semiconductor to be the semiconductor 406 b is formed. The semiconductor to be the semiconductor 406 b can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. Note that the semiconductor to be the semiconductor 406 a and the semiconductor to be the semiconductor 406 b are successively formed without being exposed to the air, in which case impurities can be prevented from entering the films and the interface therebetween.

Next, heat treatment is preferably performed. The heat treatment can reduce hydrogen concentration in the semiconductor to be the semiconductor 406 a and in the semiconductor to be the semiconductor 406 b in some cases. In addition, the heat treatment can reduce oxygen vacancies in the semiconductor to be the semiconductor 406 a and in the semiconductor to be the semiconductor 406 b in some cases. The heat treatment may be performed at higher than or equal to 250° C. and lower than or equal to 650° C., preferably higher than or equal to 450° C. and lower than or equal to 600° C., more preferably higher than or equal to 520° C. and lower than or equal to 570° C. The heat treatment is performed in an inert gas atmosphere or an atmosphere containing an oxidizing gas at 10 ppm or more, 1% or more, or 10% or more. The heat treatment may be performed under a reduced pressure. Alternatively, the heat treatment may be performed in such a manner that heat treatment is performed in an inert gas atmosphere, and then another heat treatment is performed in an atmosphere containing an oxidizing gas at 10 ppm or more, 1% or more, or 10% or more in order to compensate desorbed oxygen. By the heat treatment, crystallinity of the semiconductor to be the semiconductor 406 a and crystallinity of the semiconductor to be the semiconductor 406 b can be increased and impurities such as hydrogen and water can be removed.

Then, a resist or the like is formed over the semiconductor to be the semiconductor 406 b and processing is performed using the resist, whereby the semiconductor 406 a and the semiconductor 406 b are formed (see FIGS. 3A and 3B).

Next, a conductor is formed. The conductor can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

The conductor may be formed to have a single-layer structure or a stacked-layer structure including a conductor containing, for example, one or more kinds of boron, nitrogen, oxygen, fluorine, silicon, phosphorus, aluminum, titanium, chromium, manganese, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, molybdenum, ruthenium, silver, indium, tin, tantalum, and tungsten. An alloy or a compound of the above element may be used, for example, and a conductor containing aluminum, a conductor containing copper and titanium, a conductor containing copper and manganese, a conductor containing indium, tin, and oxygen, a conductor containing titanium and nitrogen, or the like may be used.

Next, a resist or the like is formed over the conductor, and the conductor is processed into a conductor 416 a and a conductor 416 b using the resist (see FIGS. 4A and 4B).

For example, when the conductor 413, the insulator 402, the conductor 416 a, and the conductor 416 b serve as a gate electrode, a gate insulator, a source electrode, and a drain electrode, respectively, a bottom-gate transistor may be obtained by completing the steps up to FIGS. 4A and 4B.

Next, a semiconductor 436 c is formed. The semiconductor 436 c can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. Before the formation of the semiconductor 436 c, surfaces of the semiconductor 406 a, the semiconductor 406 b, the conductor 416 a, and the conductor 416 b may be etched. For example, plasma containing a rare gas can be used for the etching. After that, the semiconductor 436 c is successively formed without being exposed to the air, whereby impurities can be prevented from entering interfaces between the semiconductor 436 c and the semiconductor 406 a, the semiconductor 406 b, the conductor 416 a, or the conductor 416 b. In some cases, impurities at an interface between films are diffused more easily than impurities in a film. For this reason, a reduction in impurity at the interfaces leads to stable electrical characteristics of a transistor.

Next, an insulator 442 is formed. The insulator 442 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. Note that the semiconductor 436 c and the insulator 442 are successively formed without being exposed to the air, in which case impurities can be prevented from entering the films and the interface therebetween.

The insulator 442 may have a single-layer structure or a stacked-layer structure including an insulator containing, for example, boron, carbon, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon, phosphorus, chlorine, argon, gallium, germanium, yttrium, zirconium, lanthanum, neodymium, hafnium, or tantalum. The insulator 442 may be formed using aluminum oxide, magnesium oxide, silicon oxide, silicon oxynitride, silicon nitride oxide, silicon nitride, gallium oxide, germanium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, or tantalum oxide.

Next, fluorine ions may be added to the insulator 442 so that the insulator 442 includes excess oxygen and a hydrogen trap. The addition of fluorine ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 5 kV and less than or equal to 200 kV, preferably greater than or equal to 20 kV and less than or equal to 100 kV at a dose of greater than or equal to 1×10¹⁴ ions/cm′ and less than or equal to 5×10¹⁶ ions/cm′, preferably greater than or equal to 5×10¹⁴ ions/cm² and less than or equal to 1×10¹⁶ ions/cm², for example.

Next, a conductor 434 is formed (see FIGS. 5A and 5B). The conductor 434 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. Note that the insulator 442 and the conductor 434 are successively formed without being exposed to the air, in which case impurities can be prevented from entering the films and the interface therebetween.

The conductor 434 may be formed to have a single-layer structure or a stacked-layer structure including a conductor containing, for example, one or more kinds of boron, nitrogen, oxygen, fluorine, silicon, phosphorus, aluminum, titanium, chromium, manganese, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, molybdenum, ruthenium, silver, indium, tin, tantalum, and tungsten. An alloy or a compound of the above element may be used, for example, and a conductor containing aluminum, a conductor containing copper and titanium, a conductor containing copper and manganese, a conductor containing indium, tin, and oxygen, a conductor containing titanium and nitrogen, or the like may be used.

Then, a resist or the like is formed over the conductor 434 and the conductor 434 is processed into a conductor 404 using the resist. The insulator 442 is processed into an insulator 412 using the resist or the conductor 404. The semiconductor 436 c is processed into a semiconductor 406 c using the resist, the conductor 404, or the insulator 412 (see FIGS. 6A and 6B). The semiconductor 406 c, the insulator 412, and the conductor 404 have the same shape when seen from the above, but a transistor of one embodiment of the present invention is not limited to this shape. For example, the semiconductor 406 c, the insulator 412, and the conductor 404 may be processed using different resists. For example, after the insulator 412 is formed, the conductor to be the conductor 404 may be formed; or after the conductor 404 is formed, a resist or the like may be formed over the insulator to be the insulator 412. For example, the semiconductor 406 c may be shared between adjacent transistors or the like.

Next, an insulator may be formed. The insulator can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

The insulator may be formed to have a single-layer structure or a stacked-layer structure including an insulator containing, for example, boron, carbon, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon, phosphorus, chlorine, argon, gallium, germanium, yttrium, zirconium, lanthanum, neodymium, hafnium, or tantalum. The insulator may be formed to have a single-layer structure or a stacked-layer structure including an insulator containing, for example, aluminum oxide, silicon nitride oxide, silicon nitride, gallium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, or tantalum oxide.

The insulator preferably has a function of a barrier layer. The insulator has, for example, a function of blocking oxygen and/or hydrogen. Alternatively, the insulator preferably has a higher capability of blocking oxygen and/or hydrogen than the insulator 402 and the insulator 412, for example.

Next, fluorine ions may be added to the insulator so that the insulator includes excess oxygen and a hydrogen trap. The addition of fluorine ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 5 kV and less than or equal to 200 kV, preferably greater than or equal to 20 kV and less than or equal to 100 kV at a dose of greater than or equal to 1×10¹⁴ ions/cm² and less than or equal to 5×10¹⁶ ions/cm′, preferably greater than or equal to 5×10¹⁴ ions/cm′ and less than or equal to 1×10¹⁶ ions/cm², for example.

Through the above process, the transistor of one embodiment of the present invention can be manufactured.

In the transistor illustrated in FIG. 6B, the insulator 402 and/or the insulator 442 include/includes excess oxygen and a hydrogen trap. Thus, oxygen vacancies or hydrogen in the semiconductor 406 a, the semiconductor 406 b, or the semiconductor 406 c can be reduced. Accordingly, a transistor with excellent electrical characteristics can be provided.

As illustrated in FIG. 6B, the semiconductor 406 b can be electrically surrounded by an electric field of the conductor 404 and the conductor 413 (a structure in which a semiconductor is electrically surrounded by an electric field of a conductor is referred to as a surrounded channel (s-channel) structure). Therefore, a channel is formed in the entire semiconductor 406 (the top, bottom, and side surfaces). In the s-channel structure, a large amount of current can flow between a source and a drain of the transistor, so that a high on-state current can be achieved.

In the case where the transistor has the s-channel structure, a channel is formed also in the side surface of the semiconductor 406 b. Therefore, as the semiconductor 406 b has a larger thickness, the channel region becomes larger. In other words, the thicker the semiconductor 406 b is, the larger the on-state current of the transistor is. In addition, when the semiconductor 406 b is thicker, the proportion of the region with a high carrier controllability increases, leading to a smaller subthreshold swing value. For example, the semiconductor 406 b has a region with a thickness greater than or equal to 20 nm, preferably greater than or equal to 40 nm, further preferably greater than or equal to 60 nm, still further preferably greater than or equal to 100 nm. In addition, to prevent a decrease in the productivity of the semiconductor device, the semiconductor 406 b has a region with a thickness, for example, less than or equal to 300 nm, preferably less than or equal to 200 nm, further preferably less than or equal to 150 nm.

The s-channel structure is suitable for a miniaturized transistor because a high on-state current can be achieved. A semiconductor device including the miniaturized transistor can have a high integration degree and high density. For example, the transistor includes a region having a channel length of preferably less than or equal to 40 nm, further preferably less than or equal to 30 nm, still further preferably less than or equal to 20 nm and a region having a channel width of preferably less than or equal to 40 nm, further preferably less than or equal to 30 nm, still further preferably less than or equal to 20 nm.

Note that the conductor 413 is not necessarily formed (see FIG. 7A).

Furthermore, an edge of the insulator 412 and an edge of the semiconductor 406 c may extend beyond an edge of the conductor 404 (see FIG. 7B). The insulator 442 and the semiconductor 436 c are not necessarily processed (see FIG. 7C). In the A1-A2 cross section, the width of the conductor 413 may be larger than that of the semiconductor 406 b (see FIG. 8A). The conductor 413 may be in contact with the conductor 404 through an opening (see FIG. 8B). The conductor 404 is not necessarily formed (see FIG. 8C).

<Semiconductor>

By placing the semiconductor 406 a over the semiconductor 406 b and placing the semiconductor 406 c under the semiconductor 406 b, electrical characteristics of the transistor can be increased in some cases.

The semiconductor 406 b is an oxide semiconductor containing indium, for example. The oxide semiconductor 406 b can have high carrier mobility (electron mobility) by containing indium, for example. The semiconductor 406 b preferably contains an element M. The element M is preferably aluminum, gallium, yttrium, tin, or the like. Other elements which can be used as the element M are boron, silicon, titanium, iron, nickel, germanium, zirconium, molybdenum, lanthanum, cerium, neodymium, hafnium, tantalum, tungsten, and the like. Note that two or more of the above elements may be used in combination as the element M. The element M is an element having high bonding energy with oxygen, for example. The element M is an element whose bonding energy with oxygen is higher than that of indium. The element M is an element that can increase the energy gap of the oxide semiconductor, for example. Furthermore, the semiconductor 406 b preferably contains zinc. When the oxide semiconductor contains zinc, the oxide semiconductor is easily crystallized, in some cases.

Note that the semiconductor 406 b is not limited to the oxide semiconductor containing indium. The semiconductor 406 b may be, for example, an oxide semiconductor which does not contain indium and contains zinc, an oxide semiconductor which does not contain indium and contains gallium, or an oxide semiconductor which does not contain indium and contains tin, e.g., a zinc tin oxide or a gallium tin oxide.

For the semiconductor 406 b, an oxide with a wide energy gap may be used, for example. For example, the energy gap of the semiconductor 406 b is greater than or equal to 2.5 eV and less than or equal to 4.2 eV, preferably greater than or equal to 2.8 eV and less than or equal to 3.8 eV, further preferably greater than or equal to 3 eV and less than or equal to 3.5 eV.

For example, the semiconductor 406 a and the semiconductor 406 c are oxide semiconductors including one or more elements, or two or more elements other than oxygen included in the semiconductor 406 b. Since the semiconductor 406 a and the semiconductor 406 c each include one or more elements, or two or more elements other than oxygen included in the semiconductor 406 b, a defect state is less likely to be formed at the interface between the semiconductor 406 a and the semiconductor 406 b and the interface between the semiconductor 406 b and the semiconductor 406 c.

The semiconductor 406 a, the semiconductor 406 b, and the semiconductor 406 c preferably include at least indium. In the case of using an In-M-Zn oxide as the semiconductor 406 a, when the summation of In and M is assumed to be 100 atomic %, the proportions of In and M are preferably set to be less than 50 atomic % and greater than 50 atomic %, respectively, further preferably less than 25 atomic % and greater than 75 atomic %, respectively. In the case of using an In-M-Zn oxide as the semiconductor 406 b, when the summation of In and M is assumed to be 100 atomic %, the proportions of In and M are preferably set to be greater than 25 atomic % and less than 75 atomic %, respectively, further preferably greater than 34 atomic % and less than 66 atomic %, respectively. In the case of using an In-M-Zn oxide as the semiconductor 406 c, when the summation of In and M is assumed to be 100 atomic %, the proportions of In and M are preferably set to be less than 50 atomic % and greater than 50 atomic %, respectively, further preferably less than 25 atomic % and greater than 75 atomic %, respectively. Note that the semiconductor 406 c may be an oxide that is of the same type as the oxide of the semiconductor 406 a. Note that the semiconductor 406 a and/or the semiconductor 406 c do/does not necessarily contain indium in some cases. For example, the semiconductor 406 a and/or the semiconductor 406 c may be gallium oxide. Note that the atomic ratios of the elements included in the semiconductor 406 a, the semiconductor 406 b, and the semiconductor 406 c are not necessarily simple ratios of integers.

As the semiconductor 406 b, an oxide having an electron affinity higher than those of the semiconductors 406 a and 406 c is used. For example, as the semiconductor 406 b, an oxide having an electron affinity higher than those of the semiconductors 406 a and 406 c by 0.07 eV or higher and 1.3 eV or lower, preferably 0.1 eV or higher and 0.7 eV or lower, further preferably 0.15 eV or higher and 0.4 eV or lower is used. Note that the electron affinity refers to an energy difference between the vacuum level and the conduction band minimum.

An indium gallium oxide has small electron affinity and a high oxygen-blocking property. Therefore, the semiconductor 406 c preferably includes an indium gallium oxide. The gallium atomic ratio [Ga/(In+Ga)] is, for example, higher than or equal to 70%, preferably higher than or equal to 80%, further preferably higher than or equal to 90%.

At this time, when a gate voltage is applied, a channel is formed in the semiconductor 406 b having the highest electron affinity in the semiconductors 406 a, 406 b, and 406 c.

Here, in some cases, there is a mixed region of the semiconductor 406 a and the semiconductor 406 b between the semiconductor 406 a and the semiconductor 406 b.

Furthermore, in some cases, there is a mixed region of the semiconductor 406 b and the semiconductor 406 c between the semiconductor 406 b and the semiconductor 406 c. The mixed region has a low density of defect states. For that reason, the stack including the semiconductor 406 a, the semiconductor 406 b, and the semiconductor 406 c has a band structure where energy is changed continuously at each interface and in the vicinity of the interface (continuous junction) (see FIG. 9). Note that boundaries of the semiconductor 406 a, the semiconductor 406 b, and the semiconductor 406 c are not clear in some cases.

At this time, electrons move mainly in the semiconductor 406 b, not in the semiconductor 406 a and the semiconductor 406 c. As described above, when the density of defect states at the interface between the semiconductor 406 a and the semiconductor 406 b and the density of defect states at the interface between the semiconductor 406 b and the semiconductor 406 c are decreased, electron movement in the semiconductor 406 b is less likely to be inhibited and the on-sate current of the transistor can be increased.

As factors of inhibiting electron movement are decreased, the on-state current of the transistor can be increased. For example, in the case where there is no factor of inhibiting electron movement, electrons are assumed to be efficiently moved. Electron movement is inhibited, for example, in the case where physical unevenness of the channel formation region is large.

To increase the on-state current of the transistor, for example, root mean square (RMS) roughness with a measurement area of 1 μm×1 μm of a top surface or a bottom surface (a formation surface; here, the semiconductor 406 a) of the semiconductor 406 b is less than 1 nm, preferably less than 0.6 nm, further preferably less than 0.5 nm, still further preferably less than 0.4 nm. The average surface roughness (also referred to as Ra) with the measurement area of 1 μm×1 μm is less than 1 nm, preferably less than 0.6 nm, further preferably less than 0.5 nm, still further preferably less than 0.4 nm. The maximum difference (P−V) with the measurement area of 1 μm×1 μm is less than 10 nm, preferably less than 9 nm, further preferably less than 8 nm, still further preferably less than 7 nm. RMS roughness, Ra, and P−V can be measured using a scanning probe microscope SPA-500 manufactured by SII Nano Technology Inc.

Moreover, the thickness of the semiconductor 406 c is preferably as small as possible to increase the on-state current of the transistor. For example, the semiconductor 406 c is formed to include a region having a thickness of less than 10 nm, preferably less than or equal to 5 nm, further preferably less than or equal to 3 nm. Meanwhile, the semiconductor 406 c has a function of blocking entry of elements other than oxygen (such as hydrogen and silicon) included in the adjacent insulator into the semiconductor 406 b where a channel is formed. For this reason, it is preferable that the semiconductor 406 c have a certain thickness. For example, the semiconductor 406 c is formed to include a region having a thickness of greater than or equal to 0.3 nm, preferably greater than or equal to 1 nm, further preferably greater than or equal to 2 nm. The semiconductor 406 c preferably has an oxygen blocking property to suppress outward diffusion of oxygen released from the insulator 402 and the like.

To improve reliability, preferably, the thickness of the semiconductor 406 a is large and the thickness of the semiconductor 406 c is small. For example, the semiconductor 406 a includes a region with a thickness of, for example, greater than or equal to 10 nm, preferably greater than or equal to 20 nm, further preferably greater than or equal to 40 nm, still further preferably greater than or equal to 60 nm. When the thickness of the semiconductor 406 a is made large, a distance from an interface between the adjacent insulator and the semiconductor 406 a to the semiconductor 406 b in which a channel is formed can be large. Since the productivity of the semiconductor device might be decreased, the semiconductor 406 a has a region with a thickness of, for example, less than or equal to 200 nm, preferably less than or equal to 120 nm, further preferably less than or equal to 80 nm.

For example, a region with a silicon concentration measured by secondary ion mass spectrometry (SIMS) of higher than or equal to 1×10¹⁶ atoms/cm³ and lower than or equal to 1×10¹⁹ atoms/cm³, preferably higher than or equal to 1×10¹⁶ atoms/cm³ and lower than or equal to 5×10¹⁸ atoms/cm³, further preferably higher than or equal to 1×10¹⁶ atoms/cm³ and lower than or equal to 2×10¹⁸ atoms/cm³ is provided between the semiconductor 406 b and the semiconductor 406 a. A region with a silicon concentration measured by SIMS of higher than or equal to 1×10¹⁶ atoms/cm³ and lower than or equal to 1×10¹⁹ atoms/cm³, preferably higher than or equal to 1×10¹⁶ atoms/cm³ and lower than or equal to 5×10¹⁸ atoms/cm³, further preferably higher than or equal to 1×10¹⁶ atoms/cm³ and lower than or equal to 2×10¹⁸ atoms/cm³ is provided between the semiconductor 406 b and the semiconductor 406 c.

The semiconductor 406 b includes a region with a hydrogen concentration measured by SIMS of higher than or equal to 1×10¹⁶ atoms/cm³ and lower than or equal to 2×10²⁰ atoms/cm³, preferably higher than or equal to 1×10¹⁶ atoms/cm³ and lower than or equal to 5×10¹⁹ atoms/cm³, further preferably higher than or equal to 1×10¹⁶ atoms/cm³ and lower than or equal to 1×10¹⁹ atoms/cm³, or still further preferably higher than or equal to 1×10¹⁶ atoms/cm³ and lower than or equal to 5×10¹⁸ atoms/cm³. It is preferable to reduce the hydrogen concentration in the semiconductor 406 a and the semiconductor 406 c in order to reduce the hydrogen concentration in the semiconductor 406 b. The semiconductor 406 a and the semiconductor 406 c each include a region with a hydrogen concentration measured by SIMS of higher than or equal to 1×10¹⁶ atoms/cm³ and lower than or equal to 2×10²⁰ atoms/cm³, preferably higher than or equal to 1×10¹⁶ atoms/cm³ and lower than or equal to 5×10¹⁹ atoms/cm³, further preferably higher than or equal to 1×10¹⁶ atoms/cm³ and lower than or equal to 1×10¹⁹ atoms/cm³, or still further preferably higher than or equal to 1×10¹⁶ atoms/cm³ and lower than or equal to 5×10¹⁸ atoms/cm³. Furthermore, the semiconductor 406 b includes a region with a nitrogen concentration measured by SIMS of higher than or equal to 1×10¹⁵ atoms/cm³ and lower than or equal to 5×10¹⁹ atoms/cm³, preferably higher than or equal to 1×10¹⁵ atoms/cm³ and lower than or equal to 5×10¹⁸ atoms/cm³, further preferably higher than or equal to 1×10¹⁵ atoms/cm³ and lower than or equal to 1×10¹⁸ atoms/cm³, or still further preferably higher than or equal to 1×10¹⁵ atoms/cm³ and lower than or equal to 5×10¹⁷ atoms/cm³. It is preferable to reduce the nitrogen concentration in the semiconductor 406 a and the semiconductor 406 c in order to reduce the nitrogen concentration in the semiconductor 406 b. The semiconductor 406 a and the semiconductor 406 c includes a region with a nitrogen concentration measured by SIMS of higher than or equal to 1×10¹⁵ atoms/cm³ and lower than or equal to 5×10¹⁹ atoms/cm³, preferably higher than or equal to 1×10¹⁵ atoms/cm³ and lower than or equal to 5×10¹⁸ atoms/cm³, further preferably higher than or equal to 1×10¹⁵ atoms/cm³ and lower than or equal to 1×10¹⁸ atoms/cm³, or still further preferably higher than or equal to 1×10¹⁵ atoms/cm³ and lower than or equal to 5×10¹⁷ atoms/cm³.

The above three-layer structure is an example. For example, a two-layer structure without the semiconductor 406 a or the semiconductor 406 c may be employed. Alternatively, a four-layer structure in which any one of the semiconductors described as examples of the semiconductor 406 a, the semiconductor 406 b, and the semiconductor 406 c is provided under or over the semiconductor 406 a or under or over the semiconductor 406 c may be employed. An n-layer structure (n is an integer of 5 or more) in which one or more of the semiconductors described as examples of the semiconductor 406 a, the semiconductor 406 b, and the semiconductor 406 c is provided at two or more of the following positions: over the semiconductor 406 a, under the semiconductor 406 a, over the semiconductor 406 c, and under the semiconductor 406 c.

<Structure of Oxide Semiconductor>

A structure of an oxide semiconductor is described below.

An oxide semiconductor is classified into a single crystal oxide semiconductor and a non-single-crystal oxide semiconductor. Examples of the non-single-crystal oxide semiconductor include a c-axis aligned crystalline oxide semiconductor (CAAC-OS), a polycrystalline oxide semiconductor, a microcrystalline oxide semiconductor, and an amorphous oxide semiconductor.

From another perspective, an oxide semiconductor is classified into an amorphous oxide semiconductor and a crystalline oxide semiconductor. Examples of a crystalline oxide semiconductor include a single crystal oxide semiconductor, a CAAC-OS, a polycrystalline oxide semiconductor, and a microcrystalline oxide semiconductor.

First, a CAAC-OS is described. Note that a CAAC-OS can be referred to as an oxide semiconductor including c-axis aligned nanocrystals (CANC).

A CAAC-OS is one of oxide semiconductors having a plurality of c-axis aligned crystal parts (also referred to as pellets).

In a combined analysis image (also referred to as a high-resolution TEM image) of a bright-field image and a diffraction pattern of a CAAC-OS, which is obtained using a transmission electron microscope (TEM), a plurality of pellets can be observed. However, in the high-resolution TEM image, a boundary between pellets, that is, a grain boundary is not clearly observed. Thus, in the CAAC-OS, a reduction in electron mobility due to the grain boundary is less likely to occur.

A CAAC-OS observed with TEM is described below. FIG. 60A shows a high-resolution TEM image of a cross section of the CAAC-OS which is observed from a direction substantially parallel to the sample surface. The high-resolution TEM image is obtained with a spherical aberration corrector function. The high-resolution TEM image obtained with a spherical aberration corrector function is particularly referred to as a Cs-corrected high-resolution TEM image. The Cs-corrected high-resolution TEM image can be obtained with, for example, an atomic resolution analytical electron microscope JEM-ARM200F manufactured by JEOL Ltd.

FIG. 60B is an enlarged Cs-corrected high-resolution TEM image of a region (1) in FIG. 60A. FIG. 60B shows that metal atoms are arranged in a layered manner in a pellet. Each metal atom layer has a configuration reflecting unevenness of a surface over which the CAAC-OS is formed (hereinafter, the surface is referred to as a formation surface) or a top surface of the CAAC-OS, and is arranged parallel to the formation surface or the top surface of the CAAC-OS.

As shown in FIG. 60B, the CAAC-OS has a characteristic atomic arrangement. The characteristic atomic arrangement is denoted by an auxiliary line in FIG. 60C. FIGS. 60B and 60C prove that the size of a pellet is approximately 1 nm to 3 nm, and the size of a space caused by tilt of the pellets is approximately 0.8 nm. Therefore, the pellet can also be referred to as a nanocrystal (nc).

Here, according to the Cs-corrected high-resolution TEM images, the schematic arrangement of pellets 5100 of a CAAC-OS over a substrate 5120 is illustrated by such a structure in which bricks or blocks are stacked (see FIG. 60D). The part in which the pellets are tilted as observed in FIG. 60C corresponds to a region 5161 shown in FIG. 60D.

FIG. 61A shows a Cs-corrected high-resolution TEM image of a plane of the CAAC-OS observed from a direction substantially perpendicular to the sample surface. FIGS. 61B, 61C, and 61D are enlarged Cs-corrected high-resolution TEM images of regions (1), (2), and (3) in FIG. 61A, respectively. FIGS. 61B, 61C, and 61D indicate that metal atoms are arranged in a triangular, quadrangular, or hexagonal configuration in a pellet. However, there is no regularity of arrangement of metal atoms between different pellets.

Next, a CAAC-OS analyzed by X-ray diffraction (XRD) is described. For example, when the structure of a CAAC-OS including an InGaZnO₄ crystal is analyzed by an out-of-plane method, a peak appears at a diffraction angle (2θ) of around 31° as shown in FIG. 62A. This peak is derived from the (009) plane of the InGaZnO₄ crystal, which indicates that crystals in the CAAC-OS have c-axis alignment, and that the c-axes are aligned in a direction substantially perpendicular to the formation surface or the top surface of the CAAC-OS.

Note that in structural analysis of the CAAC-OS by an out-of-plane method, another peak may appear when 2θ is around 36°, in addition to the peak at 2θ of around 31°. The peak at 2θ of around 36° indicates that a crystal having no c-axis alignment is included in part of the CAAC-OS. It is preferable that in the CAAC-OS analyzed by an out-of-plane method, a peak appear when 2θ is around 31° and that a peak not appear when 2θ is around 36°.

On the other hand, in structural analysis of the CAAC-OS by an in-plane method in which an X-ray is incident on a sample in a direction substantially perpendicular to the c-axis, a peak appears when 2θ is around 56°. This peak is attributed to the (110) plane of the InGaZnO₄ crystal. In the case of the CAAC-OS, when analysis (φ scan) is performed with 2θ fixed at around 56° and with the sample rotated using a normal vector of the sample surface as an axis (φ axis), as shown in FIG. 62B, a peak is not clearly observed. In contrast, in the case of a single crystal oxide semiconductor of InGaZnO₄, when φ scan is performed with 2θ fixed at around 56°, as shown in FIG. 62C, six peaks which are derived from crystal planes equivalent to the (110) plane are observed. Accordingly, the structural analysis using XRD shows that the directions of a-axes and b-axes are irregularly oriented in the CAAC-OS.

Next, a CAAC-OS analyzed by electron diffraction is described. For example, when an electron beam with a probe diameter of 300 nm is incident on a CAAC-OS including an InGaZnO₄ crystal in a direction parallel to the sample surface, a diffraction pattern (also referred to as a selected-area transmission electron diffraction pattern) shown in FIG. 63A can be obtained. In this diffraction pattern, spots derived from the (009) plane of an InGaZnO₄ crystal are included. Thus, the electron diffraction also indicates that pellets included in the CAAC-OS have c-axis alignment and that the c-axes are aligned in a direction substantially perpendicular to the formation surface or the top surface of the CAAC-OS. Meanwhile, FIG. 63B shows a diffraction pattern obtained in such a manner that an electron beam with a probe diameter of 300 nm is incident on the same sample in a direction perpendicular to the sample surface. As shown in FIG. 63B, a ring-like diffraction pattern is observed. Thus, the electron diffraction also indicates that the a-axes and b-axes of the pellets included in the CAAC-OS do not have regular alignment. The first ring in FIG. 63B is considered to be derived from the (010) plane, the (100) plane, and the like of the InGaZnO₄ crystal. The second ring in FIG. 63B is considered to be derived from the (110) plane and the like.

Moreover, the CAAC-OS is an oxide semiconductor having a low density of defect states. Defects in the oxide semiconductor are, for example, a defect due to impurities and oxygen vacancies. Therefore, the CAAC-OS can be regarded as an oxide semiconductor with a low impurity concentration, or an oxide semiconductor having a small number of oxygen vacancies.

The impurity contained in the oxide semiconductor might serve as a carrier trap or serve as a carrier generation source. Furthermore, oxygen vacancies in the oxide semiconductor serve as carrier traps or serve as carrier generation sources when hydrogen is captured therein.

Note that the impurity means an element other than the main components of the oxide semiconductor, such as hydrogen, carbon, silicon, or a transition metal element. For example, an element (specifically, silicon or the like) having higher strength of bonding to oxygen than a metal element included in an oxide semiconductor extracts oxygen from the oxide semiconductor, which results in disorder of the atomic arrangement and reduced crystallinity of the oxide semiconductor. A heavy metal such as iron or nickel, argon, carbon dioxide, or the like has a large atomic radius (or molecular radius), and thus disturbs the atomic arrangement of the oxide semiconductor and decreases crystallinity.

An oxide semiconductor having a low density of defect states (a small number of oxygen vacancies) can have a low carrier density. Such an oxide semiconductor is referred to as a highly purified intrinsic or substantially highly purified intrinsic oxide semiconductor. A CAAC-OS has a low impurity concentration and a low density of defect states. That is, a CAAC-OS is likely to be highly purified intrinsic or substantially highly purified intrinsic oxide semiconductor. Thus, a transistor including a CAAC-OS rarely has negative threshold voltage (is rarely normally on). The highly purified intrinsic or substantially highly purified intrinsic oxide semiconductor has few carrier traps. An electric charge trapped by the carrier traps in the oxide semiconductor takes a long time to be released. The trapped electric charge may behave like a fixed electric charge. Thus, the transistor which includes the oxide semiconductor having a high impurity concentration and a high density of defect states might have unstable electrical characteristics. However, a transistor including a CAAC-OS has small variation in electrical characteristics and high reliability.

Since the CAAC-OS has a low density of defect states, carriers generated by light irradiation or the like are less likely to be trapped in defect states. Therefore, in a transistor using the CAAC-OS, change in electrical characteristics due to irradiation with visible light or ultraviolet light is small.

<Microcrystalline Oxide Semiconductor>

Next, a microcrystalline oxide semiconductor is described.

A microcrystalline oxide semiconductor has a region in which a crystal part is observed and a region in which a crystal part is not clearly observed in a high-resolution TEM image. In most cases, the size of a crystal part included in the microcrystalline oxide semiconductor is greater than or equal to 1 nm and less than or equal to 100 nm, or greater than or equal to 1 nm and less than or equal to 10 nm. An oxide semiconductor including a nanocrystal (nc) that is a microcrystal with a size greater than or equal to 1 nm and less than or equal to 10 nm, or a size greater than or equal to 1 nm and less than or equal to 3 nm is specifically referred to as a nanocrystalline oxide semiconductor (nc-OS). In a high-resolution TEM image of the nc-OS, for example, a grain boundary is not clearly observed in some cases. Note that there is a possibility that the origin of the nanocrystal is the same as that of a pellet in a CAAC-OS. Therefore, a crystal part of the nc-OS may be referred to as a pellet in the following description.

In the nc-OS, a microscopic region (for example, a region with a size greater than or equal to 1 nm and less than or equal to 10 nm, in particular, a region with a size greater than or equal to 1 nm and less than or equal to 3 nm) has a periodic atomic arrangement. There is no regularity of crystal orientation between different pellets in the nc-OS. Thus, the orientation of the whole film is not ordered. Accordingly, the nc-OS cannot be distinguished from an amorphous oxide semiconductor, depending on an analysis method. For example, when the nc-OS is subjected to structural analysis by an out-of-plane method with an XRD apparatus using an X-ray having a diameter larger than the size of a pellet, a peak which shows a crystal plane does not appear. Furthermore, a diffraction pattern like a halo pattern is observed when the nc-OS is subjected to electron diffraction using an electron beam with a probe diameter (e.g., 50 nm or larger) that is larger than the size of a pellet (the electron diffraction is also referred to as selected-area electron diffraction). Meanwhile, spots appear in a nanobeam electron diffraction pattern of the nc-OS when an electron beam having a probe diameter close to or smaller than the size of a pellet is applied. Moreover, in a nanobeam electron diffraction pattern of the nc-OS, regions with high luminance in a circular (ring) pattern are shown in some cases. Also in a nanobeam electron diffraction pattern of the nc-OS, a plurality of spots is shown in a ring-like region in some cases.

Since there is no regularity of crystal orientation between the pellets (nanocrystals) as mentioned above, the nc-OS can also be referred to as an oxide semiconductor including random aligned nanocrystals (RANC) or an oxide semiconductor including non-aligned nanocrystals (NANC).

The nc-OS is an oxide semiconductor that has high regularity as compared with an amorphous oxide semiconductor. Therefore, the nc-OS is likely to have a lower density of defect states than an amorphous oxide semiconductor. Note that there is no regularity of crystal orientation between different pellets in the nc-OS. Therefore, the nc-OS has a higher density of defect states than the CAAC-OS.

<Amorphous Oxide Semiconductor>

Next, an amorphous oxide semiconductor is described.

The amorphous oxide semiconductor is an oxide semiconductor having disordered atomic arrangement and no crystal part and exemplified by an oxide semiconductor which exists in an amorphous state as quartz.

In a high-resolution TEM image of the amorphous oxide semiconductor, crystal parts cannot be found.

When the amorphous oxide semiconductor is subjected to structural analysis by an out-of-plane method with an XRD apparatus, a peak which shows a crystal plane does not appear. A halo pattern is observed when the amorphous oxide semiconductor is subjected to electron diffraction. Furthermore, a spot is not observed and only a halo pattern appears when the amorphous oxide semiconductor is subjected to nanobeam electron diffraction.

There are various understandings of an amorphous structure. For example, a structure whose atomic arrangement does not have ordering at all is called a completely amorphous structure. Meanwhile, a structure which does not have long-range ordering but might have ordering in a range from an atom to the nearest neighbor atoms or to the second-nearest neighbor atoms is also called an amorphous structure. Therefore, the strictest definition does not permit an oxide semiconductor to be called an amorphous oxide semiconductor as long as even a negligible degree of ordering is present in an atomic arrangement. At least an oxide semiconductor having long-term ordering cannot be called an amorphous oxide semiconductor. Accordingly, because of the presence of crystal part, for example, a CAAC-OS and an nc-OS cannot be called an amorphous oxide semiconductor or a completely amorphous oxide semiconductor.

<Amorphous-Like Oxide Semiconductor>

Note that an oxide semiconductor may have a structure intermediate between the nc-OS and the amorphous oxide semiconductor. The oxide semiconductor having such a structure is specifically referred to as an amorphous-like oxide semiconductor (a-like OS).

In a high-resolution TEM image of the a-like OS, a void may be observed. Furthermore, in the high-resolution TEM image, there are a region where a crystal part is clearly observed and a region where a crystal part is not observed.

The a-like OS has an unstable structure because it contains a void. To verify that an a-like OS has an unstable structure as compared with a CAAC-OS and an nc-OS, a change in structure caused by electron irradiation is described below.

An a-like OS (referred to as Sample A), an nc-OS (referred to as Sample B), and a CAAC-OS (referred to as Sample C) are prepared as samples subjected to electron irradiation. Each of the samples is an In—Ga—Zn oxide.

First, a high-resolution cross-sectional TEM image of each sample is obtained. The high-resolution cross-sectional TEM images show that all the samples have crystal parts.

Note that which part is regarded as a crystal part is determined as follows. It is known that a unit cell of an InGaZnO₄ crystal has a structure in which nine layers including three In—O layers and six Ga—Zn—O layers are stacked in the c-axis direction. The distance between the adjacent layers is equivalent to the lattice spacing on the (009) plane (also referred to as d value). The value is calculated to be 0.29 nm from crystal structural analysis. Accordingly, a portion where the lattice spacing between lattice fringes is greater than or equal to 0.28 nm and less than or equal to 0.30 nm is regarded as a crystal part of InGaZnO₄. Each of lattice fringes corresponds to the a-b plane of the InGaZnO₄ crystal.

FIG. 64 shows change in the average size of crystal parts (at 22 points to 45 points) in each sample. Note that the crystal part size corresponds to the length of a lattice fringe. FIG. 64 indicates that the crystal part size in the a-like OS increases with an increase in the cumulative electron dose. Specifically, as shown by (1) in FIG. 64, a crystal part of approximately 1.2 nm (also referred to as an initial nucleus) at the start of TEM observation grows to a size of approximately 2.6 nm at a cumulative electron dose of 4.2×10⁸ e⁻/nm². In contrast, the crystal part size in the nc-OS and the CAAC-OS shows little change from the start of electron irradiation to a cumulative electron dose of 4.2×10⁸ e⁻/nm². Specifically, as shown by (2) and (3) in FIG. 64, the average crystal sizes in an nc-OS and a CAAC-OS are approximately 1.4 nm and approximately 2.1 nm, respectively, regardless of the cumulative electron dose.

In this manner, growth of the crystal part in the a-like OS is induced by electron irradiation. In contrast, in the nc-OS and the CAAC-OS, growth of the crystal part is hardly induced by electron irradiation. Therefore, the a-like OS has an unstable structure as compared with the nc-OS and the CAAC-OS.

The a-like OS has a lower density than the nc-OS and the CAAC-OS because it contains a void. Specifically, the density of the a-like OS is higher than or equal to 78.6% and lower than 92.3% of the density of the single crystal oxide semiconductor having the same composition. The density of each of the nc-OS and the CAAC-OS is higher than or equal to 92.3% and lower than 100% of the density of the single crystal oxide semiconductor having the same composition. Note that it is difficult to deposit an oxide semiconductor having a density of lower than 78% of the density of the single crystal oxide semiconductor.

For example, in the case of an oxide semiconductor having an atomic ratio of In:Ga:Zn=1:1:1, the density of single crystal InGaZnO₄ with a rhombohedral crystal structure is 6.357 g/cm³. Accordingly, in the case of the oxide semiconductor having an atomic ratio of In:Ga:Zn=1:1:1, the density of the a-like OS is higher than or equal to 5.0 g/cm³ and lower than 5.9 g/cm³. For example, in the case of the oxide semiconductor having an atomic ratio of In:Ga:Zn=1:1:1, the density of each of the nc-OS and the CAAC-OS is higher than or equal to 5.9 g/cm³ and lower than 6.3 g/cm³.

Note that there is a possibility that an oxide semiconductor having a certain composition cannot exist in a single crystal structure. In that case, single crystal oxide semiconductors with different compositions are combined at an adequate ratio, which makes it possible to calculate density equivalent to that of a single crystal oxide semiconductor with the desired composition. The density of a single crystal oxide semiconductor having the desired composition can be calculated using a weighted average according to the combination ratio of the single crystal oxide semiconductors with different compositions. Note that it is preferable to use as few kinds of single crystal oxide semiconductors as possible to calculate the density.

As described above, oxide semiconductors have various structures and various properties. Note that an oxide semiconductor may be a stacked layer including two or more films of an amorphous oxide semiconductor, an a-like OS, a microcrystalline oxide semiconductor, and a CAAC-OS, for example.

<Deposition Model>

Examples of deposition models of a CAAC-OS and an nc-OS are described below.

FIG. 65A is a schematic view of the inside of a deposition chamber where a CAAC-OS is deposited by a sputtering method.

A target 5130 is attached to a backing plate. A plurality of magnets is provided to face the target 5130 with the backing plate positioned therebetween. The plurality of magnets generates a magnetic field. A sputtering method in which the disposition rate is increased by utilizing a magnetic field of magnets is referred to as a magnetron sputtering method.

The substrate 5120 is placed to face the target 5130, and the distance d (also referred to as a target-substrate distance (T-S distance)) is greater than or equal to 0.01 m and less than or equal to 1 m, preferably greater than or equal to 0.02 m and less than or equal to 0.5 m. The deposition chamber is mostly filled with a deposition gas (e.g., an oxygen gas, an argon gas, or a mixed gas containing oxygen at 5 vol % or higher) and the pressure in the deposition chamber is controlled to be higher than or equal to 0.01 Pa and lower than or equal to 100 Pa, preferably higher than or equal to 0.1 Pa and lower than or equal to 10 Pa. Here, discharge starts by application of a voltage at a certain value or higher to the target 5130, and plasma is observed. The magnetic field forms a high-density plasma region in the vicinity of the target 5130. In the high-density plasma region, the deposition gas is ionized, so that an ion 5101 is generated. Examples of the ion 5101 include an oxygen cation (O⁺) and an argon cation (Ar⁺).

Here, the target 5130 has a polycrystalline structure which includes a plurality of crystal grains and in which a cleavage plane exists in at least one crystal grain. FIG. 66A shows a structure of an InGaZnO₄ crystal included in the target 5130 as an example. Note that FIG. 66A shows a structure of the case where the InGaZnO₄ crystal is observed from a direction parallel to the b-axis. FIG. 66A indicates that oxygen atoms in a Ga—Zn—O layer are positioned close to those in an adjacent Ga—Zn—O layer. The oxygen atoms have negative charge, whereby repulsive force is generated between the two adjacent Ga—Zn—O layers. As a result, the InGaZnO₄ crystal has a cleavage plane between the two adjacent Ga—Zn—O layers.

The ion 5101 generated in the high-density plasma region is accelerated toward the target 5130 side by an electric field, and then collides with the target 5130. At this time, a pellet 5100 a and a pellet 5100 b which are flat-plate-like (pellet-like) sputtered particles are separated and sputtered from the cleavage plane. Note that structures of the pellet 5100 a and the pellet 5100 b may be distorted by an impact of collision of the ion 5101.

The pellet 5100 a is a flat-plate-like (pellet-like) sputtered particle having a triangle plane, e.g., regular triangle plane. The pellet 5100 b is a flat-plate-like (pellet-like) sputtered particle having a hexagon plane, e.g., regular hexagon plane. Note that flat-plate-like (pellet-like) sputtered particles such as the pellet 5100 a and the pellet 5100 b are collectively called pellets 5100. The shape of a flat plane of the pellet 5100 is not limited to a triangle or a hexagon. For example, the flat plane may have a shape formed by combining two or more triangles. For example, a quadrangle (e.g., rhombus) may be formed by combining two triangles (e.g., regular triangles).

The thickness of the pellet 5100 is determined depending on the kind of deposition gas and the like. The thicknesses of the pellets 5100 are preferably uniform; the reason for this is described later. In addition, the sputtered particle preferably has a pellet shape with a small thickness as compared to a dice shape with a large thickness. For example, the thickness of the pellet 5100 is greater than or equal to 0.4 nm and less than or equal to 1 nm, preferably greater than or equal to 0.6 nm and less than or equal to 0.8 nm. In addition, for example, the width of the pellet 5100 is greater than or equal to 1 nm and less than or equal to 3 nm, preferably greater than or equal to 1.2 nm and less than or equal to 2.5 nm. The pellet 5100 corresponds to the initial nucleus in the description of (1) in FIG. 64. For example, when the ion 5101 collides with the target 5130 including an In—Ga—Zn oxide, the pellet 5100 that includes three layers of a Ga—Zn—O layer, an In—O layer, and a Ga—Zn—O layer as shown in FIG. 66B is separated. Note that FIG. 66C shows the structure of the separated pellet 5100 which is observed from a direction parallel to the c-axis. The pellet 5100 has a nanometer-sized sandwich structure including two Ga—Zn—O layers (pieces of bread) and an In—O layer (filling).

The pellet 5100 may receive a charge when passing through the plasma, so that side surfaces thereof are negatively or positively charged. In the pellet 5100, for example, an oxygen atom positioned on its side surface may be negatively charged. When the side surfaces are charged with the same polarity, charges repel each other, and accordingly, the pellet 5100 can maintain a flat-plate (pellet) shape. In the case where a CAAC-OS is an In—Ga—Zn oxide, there is a possibility that an oxygen atom bonded to an indium atom is negatively charged. There is another possibility that an oxygen atom bonded to an indium atom, a gallium atom, or a zinc atom is negatively charged. In addition, the pellet 5100 may grow by being bonded with an indium atom, a gallium atom, a zinc atom, an oxygen atom, or the like when passing through plasma. A difference in size between (2) and (1) in FIG. 64 corresponds to the amount of growth in plasma. Here, in the case where the temperature of the substrate 5120 is at around room temperature, the pellet 5100 on the substrate 5120 hardly grows; thus, an nc-OS is formed (see FIG. 65B). An nc-OS can be deposited when the substrate 5120 has a large size because the deposition of an nc-OS can be carried out at room temperature. Note that in order that the pellet 5100 grows in plasma, it is effective to increase deposition power in sputtering. High deposition power can stabilize the structure of the pellet 5100.

As shown in FIGS. 65A and 65B, the pellet 5100 flies like a kite in plasma and flutters up to the substrate 5120. Since the pellets 5100 are charged, when the pellet 5100 gets close to a region where another pellet 5100 has already been deposited, repulsion is generated. Here, above the substrate 5120, a magnetic field in a direction parallel to the top surface of the substrate 5120 (also referred to as a horizontal magnetic field) is generated. A potential difference is given between the substrate 5120 and the target 5130, and accordingly, current flows from the substrate 5120 toward the target 5130. Thus, the pellet 5100 is given a force (Lorentz force) on the top surface of the substrate 5120 by an effect of the magnetic field and the current. This is explainable with Fleming's left-hand rule.

The mass of the pellet 5100 is larger than that of an atom. Therefore, to move the pellet 5100 over the top surface of the substrate 5120, it is important to apply some force to the pellet 5100 from the outside. One kind of the force may be force which is generated by the action of a magnetic field and current. In order to apply a sufficient force to the pellet 5100 so that the pellet 5100 moves over a top surface of the substrate 5120, it is preferable to provide, on the top surface, a region where the magnetic field in a direction parallel to the top surface of the substrate 5120 is 10 G or higher, preferably 20 G or higher, further preferably 30 G or higher, still further preferably 50 G or higher. Alternatively, it is preferable to provide, on the top surface, a region where the magnetic field in a direction parallel to the top surface of the substrate 5120 is 1.5 times or higher, preferably twice or higher, further preferably 3 times or higher, still further preferably 5 times or higher as high as the magnetic field in a direction perpendicular to the top surface of the substrate 5120.

At this time, the magnets and the substrate 5120 are moved or rotated relatively, whereby the direction of the horizontal magnetic field on the top surface of the substrate 5120 continues to change. Therefore, the pellet 5100 can be moved in various directions on the top surface of the substrate 5120 by receiving forces in various directions.

Furthermore, as shown in FIG. 65A, when the substrate 5120 is heated, resistance between the pellet 5100 and the substrate 5120 due to friction or the like is low. As a result, the pellet 5100 glides above the top surface of the substrate 5120. The glide of the pellet 5100 is caused in a state where its flat plane faces the substrate 5120. Then, when the pellet 5100 reaches the side surface of another pellet 5100 that has been already deposited, the side surfaces of the pellets 5100 are bonded. At this time, the oxygen atom on the side surface of the pellet 5100 is released. With the released oxygen atom, oxygen vacancies in a CAAC-OS might be filled; thus, the CAAC-OS has a low density of defect states. Note that the temperature of the top surface of the substrate 5120 is, for example, higher than or equal to 100° C. and lower than 500° C., higher than or equal to 150° C. and lower than 450° C., or higher than or equal to 170° C. and lower than 400° C. Hence, even when the substrate 5120 has a large size, it is possible to deposit a CAAC-OS.

Furthermore, the pellet 5100 is heated on the substrate 5120, whereby atoms are rearranged, and the structure distortion caused by the collision of the ion 5101 can be reduced. The pellet 5100 whose structure distortion is reduced is substantially single crystal. Even when the pellets 5100 are heated after being bonded, expansion and contraction of the pellet 5100 itself hardly occur, which is caused by turning the pellet 5100 into substantially single crystal. Thus, formation of defects such as a grain boundary due to expansion of a space between the pellets 5100 can be prevented, and accordingly, generation of crevasses can be prevented.

The CAAC-OS does not have a structure like a board of a single crystal oxide semiconductor but has arrangement with a group of pellets 5100 (nanocrystals) like stacked bricks or blocks. Furthermore, a grain boundary does not exist between the pellets 5100. Therefore, even when deformation such as shrink occurs in the CAAC-OS owing to heating during deposition, heating or bending after deposition, it is possible to relieve local stress or release distortion. Therefore, this structure is suitable for a flexible semiconductor device. Note that the nc-OS has arrangement in which pellets 5100 (nanocrystals) are randomly stacked.

When the target 5130 is sputtered with the ion 5101, in addition to the pellets 5100, zinc oxide or the like may be separated. The zinc oxide is lighter than the pellet 5100 and thus reaches the top surface of the substrate 5120 before the pellet 5100. As a result, the zinc oxide forms a zinc oxide layer 5102 with a thickness greater than or equal to 0.1 nm and less than or equal to 10 nm, greater than or equal to 0.2 nm and less than or equal to 5 nm, or greater than or equal to 0.5 nm and less than or equal to 2 nm. FIGS. 67A to 67D are cross-sectional schematic views.

As illustrated in FIG. 67A, a pellet 5105 a and a pellet 5105 b are deposited over the zinc oxide layer 5102. Here, side surfaces of the pellet 5105 a and the pellet 5105 b are in contact with each other. In addition, a pellet 5105 c is deposited over the pellet 5105 b, and then glides over the pellet 5105 b. Furthermore, a plurality of particles 5103 separated from the target together with the zinc oxide is crystallized by heat from the substrate 5120 to form a region 5105 a 1 on another side surface of the of the pellet 5105 a. Note that the plurality of particles 5103 may contain oxygen, zinc, indium, gallium, or the like.

Then, as illustrated in FIG. 67B, the region 5105 a 1 grows to part of the pellet 5105 a to form a pellet 5105 a 2. In addition, a side surface of the pellet 5105 c is in contact with another side surface of the pellet 5105 b.

Next, as illustrated in FIG. 67C, a pellet 5105 d is deposited over the pellet 5105 a 2 and the pellet 5105 b, and then glides over the pellet 5105 a 2 and the pellet 5105 b. Furthermore, a pellet 5105 e glides toward another side surface of the pellet 5105 c over the zinc oxide layer 5102.

Then, as illustrated in FIG. 67D, the pellet 5105 d is placed so that a side surface of the pellet 5105 d is in contact with a side surface of the pellet 5105 a 2. Furthermore, a side surface of the pellet 5105 e is in contact with another side surface of the pellet 5105 c. A plurality of particles 5103 separated from the target 5130 together with the zinc oxide is crystallized by heat from the substrate 5120 to form a region 5105 d 1 on another side surface of the pellet 5105 d.

As described above, deposited pellets are placed to be in contact with each other and then growth is caused at side surfaces of the pellets, whereby a CAAC-OS is formed over the substrate 5120. Therefore, each pellet of the CAAC-OS is larger than that of the nc-OS. A difference in size between (3) and (2) in FIG. 64 corresponds to the amount of growth after deposition.

When spaces between pellets are extremely small, the pellets may form a large pellet. The large pellet has a single crystal structure. For example, the size of the pellet may be greater than or equal to 10 nm and less than or equal to 200 nm, greater than or equal to 15 nm and less than or equal to 100 nm, or greater than or equal to 20 nm and less than or equal to 50 nm, when seen from the above. In this case, in an oxide semiconductor used for a minute transistor, a channel formation region might be fit inside the large pellet. That is, the region having a single crystal structure can be used as the channel formation region. Furthermore, when the size of the pellet is increased, the region having a single crystal structure can be used as the channel formation region, the source region, and the drain region of the transistor.

In this manner, when the channel formation region or the like of the transistor is formed in a region having a single crystal structure, the frequency characteristics of the transistor can be increased in some cases.

As shown in such a model, the pellets 5100 are considered to be deposited on the substrate 5120. Thus, a CAAC-OS can be deposited even when a formation surface does not have a crystal structure; therefore, a growth mechanism in this case is different from epitaxial growth. In addition, laser crystallization is not needed for formation of a CAAC-OS, and a uniform film can be formed even over a large-sized glass substrate or the like. For example, even when the top surface (formation surface) of the substrate 5120 has an amorphous structure (e.g., the top surface is formed of amorphous silicon oxide), a CAAC-OS can be formed.

In addition, it is found that in formation of the CAAC-OS, the pellets 5100 are arranged in accordance with the top surface shape of the substrate 5120 that is the formation surface even when the formation surface has unevenness. For example, in the case where the top surface of the substrate 5120 is flat at the atomic level, the pellets 5100 are arranged so that flat planes parallel to the a-b plane face downwards. In the case where the thicknesses of the pellets 5100 are uniform, a layer with a uniform thickness, flatness, and high crystallinity is formed. By stacking n layers (n is a natural number), the CAAC-OS can be obtained.

In the case where the top surface of the substrate 5120 has unevenness, a CAAC-OS in which n layers (n is a natural number) in each of which the pellets 5100 are arranged along the unevenness are stacked is formed. Since the substrate 5120 has unevenness, a gap is easily generated between the pellets 5100 in the CAAC-OS in some cases. Note that, even in such a case, owing to intermolecular force, the pellets 5100 are arranged so that a gap between the pellets is as small as possible even on the unevenness surface. Therefore, even when the formation surface has unevenness, a CAAC-OS with high crystallinity can be obtained.

Since a CAAC-OS is deposited in accordance with such a model, the sputtered particle preferably has a pellet shape with a small thickness. Note that when the sputtered particles have a dice shape with a large thickness, planes facing the substrate 5120 vary; thus, the thicknesses and orientations of the crystals cannot be uniform in some cases.

According to the deposition model described above, a CAAC-OS with high crystallinity can be formed even on a formation surface with an amorphous structure.

<Silicon Oxide Including Fluorine>

As an example of the insulator including excess oxygen and/or a hydrogen trap, a silicon oxide including fluorine is described below with reference to FIGS. 1A to 1C.

A silicon oxide (SiO₂) includes two oxygen atoms with respect to one silicon atom. As illustrated in FIG. 1A, one silicon atom is bonded to four oxygen atoms, and one oxygen atom is bonded to two silicon atoms.

When two fluorine atoms enter the silicon oxide, bonds of one oxygen atom to two silicon atoms are cut ( . . . Si—O—Si . . . +2F→ . . . Si—O—Si . . . +2F). Then, the fluorine atoms are bonded to the silicon atoms whose bonds to the oxygen atom have been cut ( . . . Si—O—Si . . . +2F→ . . . Si—F F—Si . . . +O). At this time, the oxygen atom whose bonds have been cut becomes excess oxygen (see FIG. 1B).

The excess oxygen included in silicon oxide can reduce oxygen vacancies in the oxide semiconductor. Oxygen vacancies in the oxide semiconductor serve as hole traps or the like. Accordingly, excess oxygen included in silicon oxide can lead to stable electrical characteristics of the transistor.

Furthermore, when one fluorine atom and one hydrogen atom enter silicon oxide, a bond of one of four oxygen atoms bonded to one silicon atom is cut ( . . . Si—O—Si . . . +F+H→ . . . Si—O—Si . . . +F+H). Then, the fluorine atom is bonded to the silicon atom whose bond to the oxygen atom has been cut ( . . . Si—O—Si . . . +F+H→ . . . Si—F—O—Si . . . +H). Then, the oxygen atom having been bonded to the silicon atom is bonded to the hydrogen atom and is terminated ( . . . Si—F—O—Si . . . +H→ . . . Si—F H—O—Si . . . ; see FIG. 1C).

When silicon oxide includes hydrogen traps, the hydrogen concentration of the oxide semiconductor can be reduced. Note that hydrogen is an impurity in the oxide semiconductor. For example, when hydrogen enters oxygen vacancy sites in an oxide semiconductor, electrons serving as carriers might be generated. Thus, when silicon oxide includes hydrogen traps, the carrier density in the channel formation region can be lowered; as a result, the threshold voltage of the transistor can be shifted in the positive direction by the amount corresponding to the reduction of the carrier density. In other words, the transistor can have electrical characteristics close to normally-off characteristics. Hydrogen trapped in silicon oxide requires high energy to be eliminated. Accordingly, elimination of the trapped hydrogen is hard to occur in silicon oxide.

As described above, when fluorine is included in silicon oxide, generation of excess oxygen and/or the trap of hydrogen occurs. Note that in the case where excess oxygen is consumed to reduce oxygen vacancies in the oxide semiconductor, the amount of oxygen in the silicon oxide becomes smaller than that before fluorine enters the silicon oxide. In the case where hydrogen from the oxide semiconductor is trapped, the amount of hydrogen in the silicon oxide becomes larger than that before fluorine enters the silicon oxide.

In order for the transistor to have stable electrical characteristics which are close to normally-off characteristics, excess oxygen and hydrogen traps are set at adequate amounts, which are attained for example by setting the fluorine concentration higher than the hydrogen concentration in the silicon oxide. Note that the fluorine concentration and the hydrogen concentration in the silicon oxide can be compared by SIMS, Rutherford backscattering spectrometry (RBS), and hydrogen forward scattering (HFS), for example.

<Heat Treatment>

Here, a method for controlling a furnace used for the heat treatment is described with reference to FIGS. 68A to 68C. Note that an atmosphere used for the heat treatment described here is an example and can be changed as appropriate.

FIG. 68A shows an example where heat treatment is performed twice in different atmospheres. First, an object is put in a furnace. Next, a nitrogen gas is added into the furnace, and the temperature in the furnace is set at a first temperature. The first temperature is increased to a second temperature in one hour. The second temperature is kept for one hour. The second temperature is decreased to a third temperature in one hour. Next, a nitrogen gas and an oxygen gas are added into the furnace. The third temperature is kept for one hour. The third temperature is increased to a fourth temperature in one hour. The fourth temperature is kept for one hour. The fourth temperature is decreased to a fifth temperature in one hour. Then, the object is taken out from the furnace.

The first temperature, the third temperature, and the fifth temperature are in a temperature range at which the object can be put in and taken out from the furnace (e.g., higher than or equal to 50° C. and lower than or equal to 200° C.). If the first temperature, the third temperature, and the fifth temperature are too low, it takes a long time to decrease the temperature, which might decline the productivity. If the first temperature and the fifth temperature are too high, the object might be damaged when being put in or taken out from the furnace. The second temperature and the fourth temperature are the maximum temperatures of the heat treatment in the respective atmospheres (e.g., higher than or equal to 250° C. and lower than or equal to 650° C.). In this specification, the time of heat treatment means the time during which the maximum temperature is maintained in each atmosphere.

By the method shown in FIG. 68A, the total time is seven hours in the case where two kinds of atmospheres are employed and each heat treatment is performed for one hour.

FIG. 68B shows an example where heat treatment is performed once without changing the atmosphere. First, an object is put in a furnace. Next, clean dry air (CDA) is added into the furnace, and the temperature in the furnace is set at a sixth temperature. CDA is an air having a water content of less than or equal to 20 ppm, less than or equal to 1 ppm, or less than or equal to 10 ppb. The sixth temperature is increased to a seventh temperature in one hour. The seventh temperature is kept for two hours. The seventh temperature is decreased to an eighth temperature in one hour. Then, the object is taken out from the furnace.

The sixth temperature and the eighth temperature are in a temperature range at which the object can be put in and taken out from the furnace. The seventh temperature is the maximum temperature of the heat treatment.

By the method shown in FIG. 68B, the total time is four hours in the case where one kind of atmosphere is employed and heat treatment is performed for two hours.

FIG. 68C shows an example where heat treatment is performed once in different atmospheres. First, an object is put in a furnace. Next, a nitrogen gas is added into the furnace, and the temperature in the furnace is set at a ninth temperature. The ninth temperature is increased to a tenth temperature in one hour. The tenth temperature is kept for one hour. Next, CDA is added into the furnace. The tenth temperature is kept for one hour. The tenth temperature is decreased to an eleventh temperature in one hour. Then, the object is taken out from the furnace.

The ninth temperature and the eleventh temperature are in a temperature range at which the object can be put in and taken out from the furnace. The tenth temperature is the maximum temperature of the heat treatment in the respective atmospheres.

By the method shown in FIG. 68C, the total time is four hours in the case where two kinds of atmospheres are employed and heat treatment is performed for two hours.

The time for the heat treatment by the methods shown in FIGS. 68B and 68C can be shorter than that by the method shown in FIG. 68A. Thus, semiconductor devices can be manufactured with high productivity.

<Transistor 2>

A transistor of one embodiment of the present invention is described below.

FIG. 10A, FIG. 11A, FIG. 12A, FIG. 13A, and FIG. 14A are top views illustrating a method for manufacturing a transistor. The dashed-dotted line B1-B2 and the dashed-dotted line B3-B4 are shown in each top view, and FIG. 10B, FIG. 11B, FIG. 12B, FIG. 13B, and FIG. 14B are cross-sectional views taken along the dashed-dotted line B1-B2 and the dashed-dotted line B3-B4.

First, the substrate 400 is prepared.

Next, a conductor is formed. The conductor may be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, a resist or the like is formed over the conductor and the conductor is processed into the conductor 413 using the resist. Note that the case where the resist is simply formed also includes the case where a BARC is formed below the resist.

Then, the insulator 402 is formed (see FIGS. 10A and 10B). The insulator 402 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, fluorine ions may be added to the insulator 402 so that the insulator 402 includes excess oxygen and a hydrogen trap. The addition of fluorine ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 2 kV and less than or equal to 100 kV, preferably greater than or equal to 5 kV and less than or equal to 50 kV at a dose of greater than or equal to 1×10¹⁴ ions/cm² and less than or equal to 5×10¹⁶ ions/cm², preferably greater than or equal to 5×10¹⁴ ions/cm² and less than or equal to 1×10¹⁶ ions/cm², for example.

Here, in the case where the insulator 402 has a stacked structure formed by forming a first insulator and a second insulator in this order, addition of fluorine ions is preferably performed such that the first insulator has a higher concentration than the second insulator. That is, addition of fluorine ions is preferably performed such that the second insulator has a lower concentration than the first insulator. Thus, added fluorine can be prevented from entering a semiconductor to be formed later. For example, an increase in carrier density caused by fluorine in the semiconductor can be inhibited in some cases. The second insulator preferably has oxygen permeability. For example, the second insulator preferably has higher oxygen permeability than the semiconductor 406 a to be formed later.

The insulator 402 preferably has a hydrogen-blocking property. For example, the insulator 402 preferably has a higher hydrogen-blocking property than the insulator 412 to be formed later. The insulator 402 having a hydrogen-blocking property can prevent hydrogen from entering the semiconductor 406 a, the semiconductor 406 b, and the like which are to be formed later. Thus, a transistor having excellent electrical characteristics can be provided.

Next, a semiconductor to be the semiconductor 406 a is formed. The semiconductor to be the semiconductor 406 a can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, oxygen ions may be added so that a semiconductor to be the semiconductor 406 a includes excess oxygen. The addition of oxygen ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 2 kV and less than or equal to 10 kV at a dose of greater than or equal to 5×10¹⁴ ions/cm² and less than or equal to 5×10¹⁶ ions/cm², for example.

Next, fluorine ions may be added to the insulator 402 so that the insulator 402 includes excess oxygen and a hydrogen trap. The addition of fluorine ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 5 kV and less than or equal to 200 kV, preferably greater than or equal to 20 kV and less than or equal to 100 kV at a dose of greater than or equal to 1×10¹⁴ ions/cm² and less than or equal to 5×10¹⁶ ions/cm², preferably greater than or equal to 5×10¹⁴ ions/cm² and less than or equal to 1×10¹⁶ ions/cm², for example. Note that the addition of oxygen ions to the semiconductor to be the semiconductor 406 a and the addition of fluorine ions to the insulator 402 may be performed in reverse order.

Next, a semiconductor to be the semiconductor 406 b is formed. The semiconductor to be the semiconductor 406 b can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. Note that the semiconductor to be the semiconductor 406 a and the semiconductor to be the semiconductor 406 b are successively formed without being exposed to the air, in which case impurities can be prevented from entering the films and the interface therebetween.

Next, heat treatment is preferably performed. The heat treatment can reduce hydrogen concentration in the semiconductor to be the semiconductor 406 a and in the semiconductor to be the semiconductor 406 b in some cases. In addition, the heat treatment can reduce oxygen vacancies in the semiconductor to be the semiconductor 406 a and in the semiconductor to be the semiconductor 406 b in some cases. The heat treatment may be performed at higher than or equal to 250° C. and lower than or equal to 650° C., preferably higher than or equal to 450° C. and lower than or equal to 600° C., more preferably higher than or equal to 520° C. and lower than or equal to 570° C. The heat treatment is performed in an inert gas atmosphere or an atmosphere containing an oxidizing gas at 10 ppm or more, 1% or more, or 10% or more. The heat treatment may be performed under a reduced pressure. Alternatively, the heat treatment may be performed in such a manner that heat treatment is performed in an inert gas atmosphere, and then another heat treatment is performed in an atmosphere containing an oxidizing gas at 10 ppm or more, 1% or more, or 10% or more in order to compensate desorbed oxygen. By the heat treatment, crystallinity of the semiconductor to be the semiconductor 406 a and crystallinity of the semiconductor to be the semiconductor 406 b can be increased and impurities such as hydrogen and water can be removed.

Then, a resist or the like is formed over the semiconductor to be the semiconductor 406 b and processing is performed using the resist, whereby the semiconductor 406 a and the semiconductor 406 b are formed (see FIGS. 11A and 11B).

Next, a conductor is formed. The conductor can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, a resist or the like is formed over the conductor, and the conductor is processed into a conductor 416 a and a conductor 416 b using the resist (see FIGS. 12A and 12B).

For example, when the conductor 413, the insulator 402, the conductor 416 a, and the conductor 416 b serve as a gate electrode, a gate insulator, a source electrode, and a drain electrode, respectively, a bottom-gate transistor may be obtained by completing the steps up to FIGS. 12A and 12B.

Next, the insulator 412 is formed. The insulator 412 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. Before the formation of the insulator 412, surfaces of the semiconductor 406 a, the semiconductor 406 b, the conductor 416 a, and the conductor 416 b may be etched. For example, plasma containing a rare gas can be used for the etching. After that, the insulator 412 is successively formed without being exposed to the air, whereby impurities can be prevented from entering interfaces between the insulator 412 and the semiconductor 406 a, the semiconductor 406 b, the conductor 416 a, or the conductor 416 b. In some cases, impurities at an interface between films are diffused more easily than impurities in a film. For this reason, a reduction in impurity at the interfaces leads to stable electrical characteristics of a transistor.

Next, an insulator 422 is formed (see FIGS. 13A and 13B). The insulator 422 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. Note that the insulator 412 and the insulator 422 are successively formed without being exposed to the air, in which case impurities can be prevented from entering the films and the interface therebetween.

The insulator 422 may have a single-layer structure or a stacked-layer structure including an insulator containing, for example, boron, carbon, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon, phosphorus, chlorine, argon, gallium, germanium, yttrium, zirconium, lanthanum, neodymium, hafnium, or tantalum. The insulator 422 may be formed using aluminum oxide, magnesium oxide, silicon oxide, silicon oxynitride, silicon nitride oxide, silicon nitride, gallium oxide, germanium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, or tantalum oxide.

Next, fluorine ions are added. The addition of fluorine ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 5 kV and less than or equal to 200 kV, preferably greater than or equal to 20 kV and less than or equal to 100 kV at a dose of greater than or equal to 1×10¹⁴ ions/cm′ and less than or equal to 5×10¹⁶ ions/cm², preferably greater than or equal to 5×10¹⁴ ions/cm² and less than or equal to 1×10¹⁶ ions/cm², for example.

The addition of fluorine ions is preferably performed such that the insulator 412 has a higher concentration than the insulator 422. That is, addition of fluorine ions is preferably performed such that the insulator 422 has a lower concentration than the insulator 412. The insulator 422 preferably has an oxygen-blocking property. For example, the insulator 422 preferably has a higher oxygen-blocking property than the insulator 412. For example, the insulator 422 may be formed with an insulator containing one or more of aluminum oxide, magnesium oxide, silicon nitride oxide, silicon nitride, gallium oxide, germanium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, and tantalum oxide. In particular, silicon nitride and silicon nitride oxide are preferred.

Next, a conductor is formed. The conductor may be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, a resist or the like is formed over the conductor, and the conductor is processed into the conductor 404 using the resist (see FIGS. 14A and 14B). The insulator 412 and/or the insulator 422 may be processed using the resist or the conductor 404.

Next, an insulator may be formed. The insulator can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

The insulator may be formed to have a single-layer structure or a stacked-layer structure including an insulator containing, for example, boron, carbon, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon, phosphorus, chlorine, argon, gallium, germanium, yttrium, zirconium, lanthanum, neodymium, hafnium, or tantalum. The insulator may be formed to have a single-layer structure or a stacked-layer structure including an insulator containing, for example, aluminum oxide, silicon nitride oxide, silicon nitride, gallium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, or tantalum oxide.

Next, fluorine ions may be added to the insulator so that the insulator includes excess oxygen and a hydrogen trap. The addition of fluorine ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 5 kV and less than or equal to 200 kV, preferably greater than or equal to 20 kV and less than or equal to 100 kV at a dose of greater than or equal to 1×10¹⁴ ions/cm² and less than or equal to 5×10¹⁶ ions/cm², preferably greater than or equal to 5×10¹⁴ ions/cm² and less than or equal to 1×10¹⁶ ions/cm², for example.

Here, in the case where the insulator has a stacked structure formed by forming a first insulator and a second insulator in this order, addition of fluorine ions is preferably performed such that the first insulator has a higher concentration than the second insulator. That is, addition of fluorine ions is preferably performed such that the second insulator has a lower concentration than the first insulator. The second insulator preferably has an oxygen-blocking property. For example, the second insulator preferably has a higher oxygen-blocking property than the first insulator.

The insulator preferably has a hydrogen-blocking property. For example, the insulator preferably has a higher hydrogen-blocking property than the insulator 402 or the insulator 412. The insulator having a hydrogen-blocking property can prevent hydrogen from entering the semiconductor 406 a, the semiconductor 406 b, and the like. Thus, a transistor having excellent electrical characteristics can be provided.

Through the above process, the transistor of one embodiment of the present invention can be manufactured.

In the transistor illustrated in FIGS. 14A and 14B, the insulator 402 and/or the insulator 412 include/includes excess oxygen and a hydrogen trap. Thus, oxygen vacancies or hydrogen in the semiconductor 406 a and/or the semiconductor 406 b can be reduced. Accordingly, a transistor with excellent electrical characteristics can be provided.

As illustrated in FIG. 14B, the transistor has an s-channel structure.

Note that the conductor 413 is not necessarily formed (see FIG. 15A). The insulator 412 and the insulator 422 may be processed to have a shape larger than that of the conductor 404, that is, an edge of the insulator 412 and an edge of the insulator 422 may extend beyond an edge of the conductor 404 (see FIG. 15B). When the conductor 404 is processed, the insulator 412 and the insulator 422 may be processed (see FIG. 15C). In the B1-B2 cross section, the width of the conductor 413 may be larger than that of the semiconductor 406 b (see FIG. 16A). The conductor 413 may be in contact with the conductor 404 through an opening (see FIG. 16B). The conductor 404 is not necessarily formed (see FIG. 16C).

Here, in some cases, there is a mixed region of the semiconductor 406 a and the semiconductor 406 b between the semiconductor 406 a and the semiconductor 406 b. The mixed region has a low density of defect states. For that reason, the stack including the semiconductor 406 a and the semiconductor 406 b has a band structure where energy is changed continuously at each interface and in the vicinity of the interface (continuous junction) (see FIG. 17A). Note that a boundary of the semiconductor 406 a and the semiconductor 406 b is not clear in some cases.

At this time, electrons move mainly in the semiconductor 406 b, not in the semiconductor 406 a. As described above, when the density of defect states at the interface between the semiconductor 406 a and the semiconductor 406 b are decreased, electron movement in the semiconductor 406 b is less likely to be inhibited and the on-sate current of the transistor can be increased. Note that the characteristics of the semiconductor 406 a and the characteristics of the semiconductor 406 b may be interchanged. The band diagram in such a case is shown in FIG. 17B.

As factors of inhibiting electron movement are decreased, the on-state current of the transistor can be increased. For example, in the case where there is no factor of inhibiting electron movement, electrons are assumed to be efficiently moved. Electron movement is inhibited, for example, in the case where physical unevenness of the channel formation region is large.

The above two-layer structure is an example. For example, a structure without the semiconductor 406 a may be employed. Alternatively, any one of semiconductors described as the semiconductor 406 a may be formed over the semiconductor 406 b. Alternatively, a three-layer structure in which any one of the semiconductors described as examples of the semiconductor 406 a and the semiconductor 406 b is provided under or over the semiconductor 406 a or under or over the semiconductor 406 b may be employed. An n-layer structure (n is an integer of 5 or more) in which one or more of the semiconductors described as examples of the semiconductor 406 a and the semiconductor 406 b is provided at two or more of the following positions: over the semiconductor 406 a, under the semiconductor 406 a, over the semiconductor 406 b, and under the semiconductor 406 b.

<Transistor 3>

Next, a method for manufacturing a transistor that is partly different from the above-described transistor is described. FIG. 18A, FIG. 19A, FIG. 20A, FIG. 21A, FIG. 22A, FIG. 23A, and FIG. 24A are top views illustrating a method for manufacturing a transistor. FIG. 18B, FIG. 19B, FIG. 20B, FIG. 21B, FIG. 22B, FIG. 23B, and FIG. 24B are each a cross-sectional view taken along dashed dotted lines F1-F2 and F3-F4 shown in the corresponding top view.

First, a substrate 500 is prepared. For the substrate 500, the description of the substrate 400 is referred to.

Next, a conductor is formed. The conductor may be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, a resist or the like is formed over the conductor and the conductor is processed into a conductor 513 using the resist. For the conductor 513, the description of the conductor 413 is referred to.

Next, an insulator is formed. The insulator can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, etching is performed from the top surface of the insulator toward the bottom surface thereof such that the etched surface is parallel to the bottom surface of the substrate 500 and the conductor 513 is exposed, whereby an insulator 503 is formed (see FIGS. 18A and 18B). When the insulator 503 is formed in this way, the top surface of the conductor 513 can be positioned at substantially the same level as the top surface of the insulator 503. Therefore, a defect in shape in a later step can be inhibited.

Then, an insulator 502 is formed (see FIGS. 19A and 19B). The insulator 502 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. For the insulator 502, the description of the insulator 402 is referred to.

Next, fluorine ions may be added to the insulator 502 so that the insulator 502 includes excess oxygen and a hydrogen trap. The addition of fluorine ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 2 kV and less than or equal to 100 kV, preferably greater than or equal to 5 kV and less than or equal to 50 kV at a dose of greater than or equal to 1×10¹⁴ ions/cm² and less than or equal to 5×10¹⁶ ions/cm², preferably greater than or equal to 5×10¹⁴ ions/cm² and less than or equal to 1×10¹⁶ ions/cm², for example.

Next, a semiconductor 536 a is formed. The semiconductor 536 a can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. For the semiconductor 536 a, the description of the semiconductor to be the semiconductor 406 a is referred to.

Next, a semiconductor 536 b is formed. The semiconductor 536 b can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. For the semiconductor 536 b, the description of the semiconductor to be the semiconductor 406 b is referred to. Note that the semiconductor 536 a and the semiconductor 536 b are successively formed without being exposed to the air, in which case impurities can be prevented from entering the films and the interface therebetween.

Next, heat treatment is preferably performed. The heat treatment may be performed at higher than or equal to 250° C. and lower than or equal to 650° C., preferably higher than or equal to 450° C. and lower than or equal to 600° C., more preferably higher than or equal to 520° C. and lower than or equal to 570° C. The heat treatment is performed in an inert gas atmosphere or an atmosphere containing an oxidizing gas at 10 ppm or more, 1% or more, or 10% or more. The heat treatment may be performed under a reduced pressure. Alternatively, the heat treatment may be performed in such a manner that heat treatment is performed in an inert gas atmosphere, and then another heat treatment is performed in an atmosphere containing an oxidizing gas at 10 ppm or more, 1% or more, or 10% or more in order to compensate desorbed oxygen. By the heat treatment, crystallinity of the semiconductor 536 a and crystallinity of the semiconductor 536 b can be increased and impurities such as hydrogen and water can be removed.

Next, a conductor is formed. The conductor can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. The description of the conductor to be the conductor 416 a and the conductor 416 b is referred to for the conductor.

Next, a resist or the like is formed over the conductor, and the conductor is processed into a conductor 516 a and a conductor 516 b using the resist (see FIGS. 20A and 20B).

Then, a resist or the like is formed over the semiconductor 536 b and processing is performed using the resist, the conductor 516 a, and the conductor 516 b, whereby a semiconductor 506 a and a semiconductor 506 b are formed (see FIGS. 21A and 21B).

Note that the conductor 516 a, the conductor 516 b, the semiconductor 506 a, and the semiconductor 506 b may be formed in the following manner after the formation of the conductor.

First, a resist or the like is formed over the conductor, and processing is performed using the resist, whereby the conductor 516, the semiconductor 506 b, and the semiconductor 506 a are formed (see FIGS. 24A and 24B). At this time, the semiconductor 506 a and the semiconductor 506 b may be formed using the conductor 516 after the resist is removed.

Next, a resist or the like is formed over the conductor 516, and the conductor is processed into the conductor 516 a and the conductor 516 b using the resist (see FIGS. 21A and 21B).

Next, a semiconductor 536 c is formed. The semiconductor 536 c can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. For the semiconductor 536 c, the description of the semiconductor 436 c is referred to.

Next, an insulator 542 is formed. The insulator 542 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. For the insulator 542, the description of the insulator 442 is referred to.

Next, fluorine ions may be added to the insulator 542 so that the insulator 542 includes excess oxygen and a hydrogen trap. The addition of fluorine ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 5 kV and less than or equal to 200 kV, preferably greater than or equal to 20 kV and less than or equal to 100 kV at a dose of greater than or equal to 1×10¹⁴ ions/cm′ and less than or equal to 5×10¹⁶ ions/cm′, preferably greater than or equal to 5×10¹⁴ ions/cm² and less than or equal to 1×10¹⁶ ions/cm², for example.

Next, a conductor 534 is formed (see FIGS. 22A and 22B). The conductor 534 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. For the conductor 534, the description of the conductor 434 is referred to.

Then, a resist or the like is formed over the conductor 534 and the conductor 534 is processed into a conductor 504 using the resist. The insulator 542 is processed into an insulator 512 using the resist or the conductor 504. The semiconductor 536 c is processed into a semiconductor 506 c using the resist, the conductor 504, or the insulator 542 (see FIGS. 23A and 23B). Note that here, the semiconductor 506 c, the insulator 512, and the conductor 504 have the same shape when seen from the above, but a transistor of one embodiment of the present invention is not limited to this shape. For example, the insulator 512 and the conductor 504 may be processed using different resists. For example, after the insulator 512 is formed, the conductor to be the conductor 504 may be formed; or after the conductor 504 is formed, a resist or the like may be formed over the insulator to be the insulator 512. For example, the semiconductor 506 c may be shared between adjacent transistors or the like.

Next, an insulator may be formed. The insulator can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

The insulator may be formed to have a single-layer structure or a stacked-layer structure including an insulator containing, for example, boron, carbon, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon, phosphorus, chlorine, argon, gallium, germanium, yttrium, zirconium, lanthanum, neodymium, hafnium, or tantalum. The insulator is preferably formed to have a single-layer structure or a stacked-layer structure including an insulator containing, for example, aluminum oxide, silicon nitride oxide, silicon nitride, gallium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, or tantalum oxide.

The insulator preferably has a function of a barrier layer. The insulator has, for example, a function of blocking oxygen and/or hydrogen. Alternatively, the insulator preferably has a higher capability of blocking oxygen and/or hydrogen than the insulator 502 and the insulator 512, for example.

Next, fluorine ions may be added to the insulator so that the insulator includes excess oxygen and a hydrogen trap. The addition of fluorine ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 5 kV and less than or equal to 200 kV, preferably greater than or equal to 20 kV and less than or equal to 100 kV at a dose of greater than or equal to 1×10¹⁴ ions/cm² and less than or equal to 5×10¹⁶ ions/cm′, preferably greater than or equal to 5×10¹⁴ ions/cm′ and less than or equal to 1×10¹⁶ ions/cm², for example.

Through the above process, the transistor of one embodiment of the present invention can be manufactured.

In the transistor illustrated in FIG. 23B, the insulator 502 and/or the insulator 512 include/includes excess oxygen and a hydrogen trap. Thus, oxygen vacancies or hydrogen in the semiconductor 506 a, the semiconductor 506 b, or the semiconductor 506 c can be reduced. Accordingly, a transistor with excellent electrical characteristics can be provided.

As illustrated in FIG. 23B, the transistor has an s-channel structure. The electric field from the conductor 504 and the conductor 513 is less likely to be inhibited by the conductor 516 a, the conductor 516 b, and the like at the side surface of the semiconductor 506 b.

Note that the conductor 513 is not necessarily formed (see FIG. 25A). Furthermore, an edge of the insulator 512 and an edge of the semiconductor 506 c may extend beyond an edge of the conductor 504 (see FIG. 25B). The insulator 542 and the semiconductor 536 c are not necessarily processed (see FIG. 25C). In the F1-F2 cross section, the width of the conductor 513 may be larger than that of the semiconductor 506 b (see FIG. 26A). The conductor 513 may be in contact with the conductor 504 through an opening (see FIG. 26B). The conductor 504 is not necessarily formed (see FIG. 26C).

<Transistor 4>

Next, a method for manufacturing a transistor that is partly different from the above-described transistor is described. FIG. 27A, FIG. 28A, FIG. 29A, FIG. 30A, FIG. 31A, FIG. 32A, and FIG. 33A are top views illustrating a method for manufacturing a transistor. FIG. 27B, FIG. 28B, FIG. 29B, FIG. 30B, FIG. 31B, FIG. 32B, and FIG. 33B are each a cross-sectional view taken along dashed dotted lines G1-G2 and G3-G4 shown in the corresponding top view.

First, the substrate 500 is prepared.

Next, a conductor is formed. The conductor may be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Then, a resist or the like is formed over the conductor, and the conductor is processed into the conductor 513 using the resist.

Next, an insulator is formed. The insulator can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, etching is performed from the top surface of the insulator toward the bottom surface thereof such that the etched surface is parallel to the bottom surface of the substrate 500 and the conductor 513 is exposed, whereby an insulator 503 is formed (see FIGS. 27A and 27B). When the insulator 503 is formed in this way, the top surface of the conductor 513 can be positioned at substantially the same level as the top surface of the insulator 503. Therefore, a defect in shape in a later step can be inhibited.

Next, the insulator 502 is formed (see FIGS. 28A and 28B). The insulator 502 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, fluorine ions may be added to the insulator 502 so that the insulator 502 includes excess oxygen and a hydrogen trap. The addition of fluorine ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 2 kV and less than or equal to 100 kV, preferably greater than or equal to 5 kV and less than or equal to 50 kV at a dose of greater than or equal to 1×10¹⁴ ions/cm′ and less than or equal to 5×10¹⁶ ions/cm′, preferably greater than or equal to 5×10¹⁴ ions/cm² and less than or equal to 1×10¹⁶ ions/cm², for example.

Here, in the case where the insulator 502 has a stacked structure formed by forming a first insulator and a second insulator in this order, addition of fluorine ions is preferably performed such that the first insulator has a higher concentration than the second insulator. That is, addition of fluorine ions is preferably performed such that the second insulator has a lower concentration than the first insulator. Thus, added fluorine can be prevented from entering a semiconductor to be formed later. For example, an increase in carrier density caused by fluorine in the semiconductor can be inhibited in some cases. The second insulator preferably has oxygen permeability. For example, the second insulator preferably has higher oxygen permeability than the semiconductor 506 a to be formed later.

The insulator 502 preferably has a hydrogen-blocking property. For example, the insulator 502 preferably has a higher hydrogen-blocking property than the insulator 512 to be formed later. The insulator 502 having a hydrogen-blocking property can prevent hydrogen from entering the semiconductor 506 a, the semiconductor 506 b, and the like which are to be formed later. Thus, a transistor having excellent electrical characteristics can be provided.

Next, the semiconductor 536 a is formed. The semiconductor 536 a can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, the semiconductor 536 b is formed. The semiconductor 536 b can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. Note that the semiconductor 536 a and the semiconductor 536 b are successively formed without being exposed to the air, in which case impurities can be prevented from entering the films and the interface therebetween.

Next, heat treatment is preferably performed. The heat treatment may be performed at higher than or equal to 250° C. and lower than or equal to 650° C., preferably higher than or equal to 450° C. and lower than or equal to 600° C., more preferably higher than or equal to 520° C. and lower than or equal to 570° C. The heat treatment is performed in an inert gas atmosphere or an atmosphere containing an oxidizing gas at 10 ppm or more, 1% or more, or 10% or more. The heat treatment may be performed under a reduced pressure. Alternatively, the heat treatment may be performed in such a manner that heat treatment is performed in an inert gas atmosphere, and then another heat treatment is performed in an atmosphere containing an oxidizing gas at 10 ppm or more, 1% or more, or 10% or more in order to compensate desorbed oxygen. By the heat treatment, crystallinity of the semiconductor 536 a and crystallinity of the semiconductor 536 b can be increased and impurities such as hydrogen and water can be removed.

Next, a conductor is formed. The conductor can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Next, a resist or the like is formed over the conductor, and processing is performed using the resist, whereby the conductor 516 a and the conductor 516 b are formed (see FIGS. 29A and 29B).

Next, a resist or the like is formed over the semiconductor 536 b, and processing is performed using the resist, the conductor 516 a, and the conductor 516 b, whereby the semiconductor 506 b and the semiconductor 506 a are formed (see FIGS. 30A and 30B).

Note that the conductor 516 a, the conductor 516 b, the semiconductor 506 a, and the semiconductor 506 b may be formed in the following manner after the formation of the conductor.

First, a resist or the like is formed over the conductor, and processing is performed using the resist, whereby the conductor 516, the semiconductor 506 b, and the semiconductor 506 a are formed (see FIGS. 33A and 33B). At this time, the semiconductor 506 a and the semiconductor 506 b may be formed using the conductor 516 after the resist is removed.

Next, a resist or the like is formed over the conductor 516, and the conductor is processed into the conductor 516 a and the conductor 516 b using the resist (see FIGS. 30A and 30B).

Next, the insulator 512 is deposited. The insulator 512 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

Then, an insulator 522 is formed (see FIGS. 31A and 31B). The insulator 522 can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. For the insulator 522, the description of the insulator 422 is referred to.

Next, fluorine ions are added. The addition of fluorine ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 5 kV and less than or equal to 200 kV, preferably greater than or equal to 20 kV and less than or equal to 100 kV at a dose of greater than or equal to 1×10¹⁴ ions/cm′ and less than or equal to 5×10¹⁶ ions/cm², preferably greater than or equal to 5×10¹⁴ ions/cm² and less than or equal to 1×10¹⁶ ions/cm², for example.

The addition of fluorine ions is preferably performed such that the insulator 512 has a higher concentration than the insulator 522. That is, addition of fluorine ions is preferably performed such that the insulator 522 has a lower concentration than the insulator 512. The insulator 522 preferably has an oxygen-blocking property. For example, the insulator 522 preferably has a higher oxygen-blocking property than the insulator 512. For example, the insulator 522 may be formed with an insulator containing one or more of aluminum oxide, magnesium oxide, silicon nitride oxide, silicon nitride, gallium oxide, germanium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, and tantalum oxide. In particular, silicon nitride and silicon nitride oxide are preferred.

Next, a conductor is formed. The conductor can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like. The description of the conductor to be the conductor 404 is referred to for the conductor.

Next, a resist or the like is formed over the conductor, and the conductor is processed into the conductor 504 using the resist (see FIGS. 32A and 32B). The insulator 512 and/or the insulator 522 may be processed using the resist or the conductor 504.

Next, an insulator may be formed. The insulator can be formed by a sputtering method, a CVD method, an MBE method, a PLD method, an ALD method, or the like.

The insulator may be formed to have a single-layer structure or a stacked-layer structure including an insulator containing, for example, boron, carbon, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon, phosphorus, chlorine, argon, gallium, germanium, yttrium, zirconium, lanthanum, neodymium, hafnium, or tantalum. The insulator may be formed to have a single-layer structure or a stacked-layer structure including an insulator containing, for example, aluminum oxide, silicon nitride oxide, silicon nitride, gallium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, or tantalum oxide.

Next, fluorine ions may be added to the insulator so that the insulator includes excess oxygen and a hydrogen trap. The addition of fluorine ions may be performed by an ion implantation method at an acceleration voltage of greater than or equal to 5 kV and less than or equal to 200 kV, preferably greater than or equal to 20 kV and less than or equal to 100 kV at a dose of greater than or equal to 1×10¹⁴ ions/cm² and less than or equal to 5×10¹⁶ ions/cm′, preferably greater than or equal to 5×10¹⁴ ions/cm′ and less than or equal to 1×10¹⁶ ions/cm², for example.

Here, in the case where the insulator has a stacked structure formed by forming a first insulator and a second insulator in this order, addition of fluorine ions is preferably performed such that the first insulator has a higher concentration than the second insulator. That is, addition of fluorine ions is preferably performed such that the second insulator has a lower concentration than the first insulator. The second insulator preferably has an oxygen-blocking property. For example, the second insulator preferably has a higher oxygen-blocking property than the first insulator.

The insulator preferably has a hydrogen-blocking property. For example, the insulator preferably has a higher hydrogen-blocking property than the insulator 402 or the insulator 412. The insulator having a hydrogen-blocking property can prevent hydrogen from entering the semiconductor 406 a, the semiconductor 406 b, and the like. Thus, a transistor having excellent electrical characteristics can be provided.

Through the above process, the transistor of one embodiment of the present invention can be manufactured.

In the transistor illustrated in FIGS. 32A and 32B, the insulator 502 and/or the insulator 512 include/includes excess oxygen and a hydrogen trap. Thus, oxygen vacancies or hydrogen in the semiconductor 506 a and/or the semiconductor 506 b can be reduced. Accordingly, a transistor with excellent electrical characteristics can be provided.

As illustrated in FIG. 32B, the transistor has an s-channel structure. The electric field from the conductor 504 and the conductor 513 is less likely to be inhibited by the conductor 516 a, the conductor 516 b, and the like at the side surface of the semiconductor 506 b.

Note that the conductor 513 is not necessarily formed (see FIG. 34A). The insulator 512 and the insulator 522 may be processed to have a shape larger than that of the conductor 504, that is, an edge of the insulator 512 and an edge of the insulator 522 may extend beyond an edge of the conductor 504 (see FIG. 34B). When the conductor 504 is processed, the insulator 512 and the insulator 522 may be processed (see FIG. 34C). In the G1-G2 cross section, the width of the conductor 513 may be larger than that of the semiconductor 506 b (see FIG. 35A). The conductor 513 may be in contact with the conductor 504 through an opening (see FIG. 35B). The conductor 504 is not necessarily formed (see FIG. 35C).

<Circuit>

An example of a circuit of a semiconductor device including a transistor or the like of one embodiment of the present invention is described below.

<CMOS Inverter>

A circuit diagram in FIG. 36A shows a configuration of a so-called CMOS inverter in which a p-channel transistor 2200 and an n-channel transistor 2100 are connected to each other in series and in which gates of them are connected to each other.

<Structure 1 of Semiconductor Device>

FIG. 37 is a cross-sectional view of the semiconductor device of FIG. 36A. The semiconductor device shown in FIG. 37 includes the transistor 2200 and the transistor 2100. The transistor 2100 is placed above the transistor 2200. Although an example where the transistor shown in FIGS. 23A and 23B is used as the transistor 2100 is shown, a semiconductor device of one embodiment of the present invention is not limited thereto. For example, any of the transistors illustrated in FIGS. 6A and 6B, FIGS. 7A to 7C, FIGS. 8A to 8C, FIGS. 25A to 25C, and FIGS. 26A to 26C can be used as the transistor 2100. Therefore, the description regarding the above-mentioned transistors is referred to for the transistor 2100 as appropriate.

The transistor 2200 shown in FIG. 37 is a transistor using a semiconductor substrate 450. The transistor 2200 includes a region 472 a in the semiconductor substrate 450, a region 472 b in the semiconductor substrate 450, an insulator 462, and a conductor 454.

In the transistor 2200, the regions 472 a and 472 b have functions of a source region and a drain region. The insulator 462 has a function of a gate insulator. The conductor 454 has a function of a gate electrode. Thus, the resistance of a channel formation region can be controlled by a potential applied to the conductor 454. In other words, conduction or non-conduction between the region 472 a and the region 472 b can be controlled by the potential applied to the conductor 454.

For the semiconductor substrate 450, a single-material semiconductor substrate of silicon, germanium, or the like or a compound semiconductor substrate of silicon carbide, silicon germanium, gallium arsenide, indium phosphide, zinc oxide, gallium oxide, or the like may be used, for example. A single crystal silicon substrate is preferably used as the semiconductor substrate 450.

For the semiconductor substrate 450, a semiconductor substrate including impurities imparting n-type conductivity is used. However, a semiconductor substrate including impurities imparting p-type conductivity may be used as the semiconductor substrate 450. In that case, a well including impurities imparting the n-type conductivity may be provided in a region where the transistor 2200 is formed. Alternatively, the semiconductor substrate 450 may be an i-type semiconductor substrate.

A top surface of the semiconductor substrate 450 preferably has a (110) plane. Thus, on-state characteristics of the transistor 2200 can be improved.

The regions 472 a and 472 b are regions including impurities imparting the p-type conductivity. Accordingly, the transistor 2200 has a structure of a p-channel transistor.

Note that the transistor 2200 is apart from an adjacent transistor by a region 460 and the like. The region 460 is an insulating region.

The semiconductor device shown in FIG. 37 includes an insulator 464, an insulator 466, an insulator 468, a conductor 480 a, a conductor 480 b, a conductor 480 c, a conductor 478 a, a conductor 478 b, a conductor 478 c, a conductor 476 a, a conductor 476 b, a conductor 474 a, a conductor 474 b, a conductor 474 c, a conductor 496 a, a conductor 496 b, a conductor 496 c, a conductor 496 d, a conductor 498 a, a conductor 498 b, a conductor 498 c, an insulator 490, an insulator 492, and an insulator 494.

The insulator 464 is placed over the transistor 2200. The insulator 466 is placed over the insulator 464. The insulator 468 is placed over the insulator 466. The insulator 490 is placed over the insulator 468. The transistor 2100 is placed over the insulator 490. The insulator 492 is placed over the transistor 2100. The insulator 494 is placed over the insulator 492.

The insulator 464 includes an opening reaching the region 472 a, an opening reaching the region 472 b, and an opening reaching the conductor 454. In the openings, the conductor 480 a, the conductor 480 b, and the conductor 480 c are embedded.

The insulator 466 includes an opening reaching the conductor 480 a, an opening reaching the conductor 480 b, and an opening reaching the conductor 480 c. In the openings, the conductor 478 a, the conductor 478 b, and the conductor 478 c are embedded.

The insulator 468 includes an opening reaching the conductor 478 b and an opening reaching the conductor 478 c. In the openings, the conductor 476 a and the conductor 476 b are embedded.

The insulator 490 includes an opening overlapping a channel formation region of the transistor 2100, an opening reaching the conductor 476 a, and an opening reaching the conductor 476 b. In the openings, the conductor 474 a, the conductor 474 b, and the conductor 474 c are embedded.

The conductor 474 a may have a function of a gate electrode of the transistor 2100. The electrical characteristics of the transistor 2100, such as the threshold voltage, may be controlled by application of a predetermined potential to the conductor 474 a, for example. The conductor 474 a may be electrically connected to the conductor 404 having a function of the gate electrode of the transistor 2100, for example. In that case, on-state current of the transistor 2100 can be increased. Furthermore, a punch-through phenomenon can be suppressed; thus, the electrical characteristics of the transistor 2100 in a saturation region can be stable.

The insulator 492 includes an opening reaching the conductor 474 b through the conductor 516 b that is one of a source electrode and a drain electrode of the transistor 2100, an opening reaching the conductor 516 a that is the other of the source electrode and the drain electrode of the transistor 2100, an opening reaching the conductor 504 that is the gate electrode of the transistor 2100, and an opening reaching the conductor 474 c. In the openings, the conductor 496 a, the conductor 496 b, the conductor 496 c, and the conductor 496 d are embedded. Note that in some cases, the openings are provided through any of components of the transistor 2100 or the like.

The insulator 494 includes an opening reaching the conductor 496 a, an opening reaching the conductor 496 b and the conductor 496 d, and an opening reaching the conductor 496 c. In the openings, the conductor 498 a, the conductor 498 b, and the conductor 498 c are embedded.

The insulators 464, 466, 468, 490, 492, and 494 may each be formed to have, for example, a single-layer structure or a stacked-layer structure including an insulator containing boron, carbon, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon, phosphorus, chlorine, argon, gallium, germanium, yttrium, zirconium, lanthanum, neodymium, hafnium, or tantalum. The insulator 401 may be formed using, for example, aluminum oxide, magnesium oxide, silicon oxide, silicon oxynitride, silicon nitride oxide, silicon nitride, gallium oxide, germanium oxide, yttrium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, hafnium oxide, or tantalum oxide.

The insulator that has a function of blocking oxygen and impurities such as hydrogen is preferably included in at least one of the insulators 464, 466, 468, 490, 492, and 494. When an insulator that has a function of blocking oxygen and impurities such as hydrogen is placed near the transistor 2100, the electrical characteristics of the transistor 2100 can be stable.

An insulator with a function of blocking oxygen and impurities such as hydrogen may be formed to have a single-layer structure or a stacked-layer structure including an insulator containing, for example, boron, carbon, nitrogen, oxygen, fluorine, magnesium, aluminum, silicon, phosphorus, chlorine, argon, gallium, germanium, yttrium, zirconium, lanthanum, neodymium, hafnium, or tantalum.

Each of the conductor 480 a, the conductor 480 b, the conductor 480 c, the conductor 478 a, the conductor 478 b, the conductor 478 c, the conductor 476 a, the conductor 476 b, the conductor 474 a, the conductor 474 b, the conductor 474 c, the conductor 496 a, the conductor 496 b, the conductor 496 c, the conductor 496 d, the conductor 498 a, the conductor 498 b, and the conductor 498 c may be formed to have, for example, a single-layer structure or a stacked-layer structure including a conductor containing one or more kinds selected from boron, nitrogen, oxygen, fluorine, silicon, phosphorus, aluminum, titanium, chromium, manganese, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, molybdenum, ruthenium, silver, indium, tin, tantalum, and tungsten. An alloy or a compound containing the above element may be used, for example, and a conductor containing aluminum, a conductor containing copper and titanium, a conductor containing copper and manganese, a conductor containing indium, tin, and oxygen, a conductor containing titanium and nitrogen, or the like may be used.

Note that a semiconductor device in FIG. 38 is the same as the semiconductor device in FIG. 37 except the structure of the transistor 2200. Therefore, the description of the semiconductor device in FIG. 37 is referred to for the semiconductor device in FIG. 38. In the semiconductor device in FIG. 38, the transistor 2200 is a FIN-type transistor. The effective channel width is increased in the FIN-type transistor 2200, whereby the on-state characteristics of the transistor 2200 can be improved. In addition, since contribution of the electric field of the gate electrode can be increased, the off-state characteristics of the transistor 2200 can be improved.

Note that a semiconductor device in FIG. 39 is the same as the semiconductor device in FIG. 37 except the structure of the transistor 2200. Therefore, the description of the semiconductor device in FIG. 37 is referred to for the semiconductor device in FIG. 39. Specifically, in the semiconductor device in FIG. 39, the transistor 2200 is formed using an SOI substrate. In the structure in FIG. 39, a region 456 is apart from the semiconductor substrate 450 with an insulator 452 provided therebetween. Since the SOI substrate is used, a punch-through phenomenon and the like can be suppressed; thus, the off-state characteristics of the transistor 2200 can be improved. Note that the insulator 452 can be formed by turning part of the semiconductor substrate 450 into an insulator. For example, silicon oxide can be used as the insulator 452.

Semiconductor devices illustrated in FIG. 40, FIG. 41, and FIG. 42 are different from the semiconductor devices illustrated in FIG. 37, FIG. 38, and FIG. 39, respectively, only in the structure of the transistor 2100. The description of the transistor illustrated in FIGS. 14A and 14B can be referred to for the transistors 2100 illustrated in FIG. 40, FIG. 41, and FIG. 42, for example.

In each of the semiconductor devices shown in FIG. 37 to FIG. 42, a p-channel transistor is formed utilizing a semiconductor substrate, and an n-channel transistor is formed above that; therefore, an occupation area of the element can be reduced. That is, the integration degree of the semiconductor device can be improved. In addition, the manufacturing process can be simplified compared to the case where an n-channel transistor and a p-channel transistor are formed utilizing the same semiconductor substrate; therefore, the productivity of the semiconductor device can be increased. Moreover, the yield of the semiconductor device can be improved. For the p-channel transistor, some complicated steps such as formation of lightly doped drain (LDD) regions, formation of a shallow trench structure, or distortion design can be omitted in some cases. Therefore, the productivity and yield of the semiconductor device can be increased in some cases, compared to a semiconductor device where an n-channel transistor is formed utilizing the semiconductor substrate.

<CMOS Analog Switch>

A circuit diagram in FIG. 36B shows a configuration in which sources of the transistors 2100 and 2200 are connected to each other and drains of the transistors 2100 and 2200 are connected to each other. With such a configuration, the transistors can function as a so-called CMOS analog switch.

<Memory Device 1>

An example of a semiconductor device (memory device) which includes the transistor of one embodiment of the present invention, which can retain stored data even when not powered, and which has an unlimited number of write cycles is shown in FIGS. 43A and 43B.

The semiconductor device illustrated in FIG. 43A includes a transistor 3200 using a first semiconductor, a transistor 3300 using a second semiconductor, and a capacitor 3400. Note that any of the above-described transistors can be used as the transistor 3300.

Note that the transistor 3300 is preferably a transistor with a low off-state current. For example, a transistor using an oxide semiconductor can be used as the transistor 3300. Since the off-state current of the transistor 3300 is low, stored data can be retained for a long period at a predetermined node of the semiconductor device. In other words, power consumption of the semiconductor device can be reduced because refresh operation becomes unnecessary or the frequency of refresh operation can be extremely low.

In FIG. 43A, a first wiring 3001 is electrically connected to a source of the transistor 3200. A second wiring 3002 is electrically connected to a drain of the transistor 3200. A third wiring 3003 is electrically connected to one of the source and the drain of the transistor 3300. A fourth wiring 3004 is electrically connected to the gate of the transistor 3300. The gate of the transistor 3200 and the other of the source and the drain of the transistor 3300 are electrically connected to the one electrode of the capacitor 3400. A fifth wiring 3005 is electrically connected to the other electrode of the capacitor 3400.

The semiconductor device in FIG. 43A has a feature that the potential of the gate of the transistor 3200 can be retained, and thus enables writing, retaining, and reading of data as follows.

Writing and retaining of data are described. First, the potential of the fourth wiring 3004 is set to a potential at which the transistor 3300 is on, so that the transistor 3300 is turned on. Accordingly, the potential of the third wiring 3003 is supplied to a node FG where the gate of the transistor 3200 and the one electrode of the capacitor 3400 are electrically connected to each other. That is, a predetermined charge is supplied to the gate of the transistor 3200 (writing). Here, one of two kinds of charges providing different potential levels (hereinafter referred to as a low-level charge and a high-level charge) is supplied. After that, the potential of the fourth wiring 3004 is set to a potential at which the transistor 3300 is off, so that the transistor 3300 is turned off. Thus, the charge is held at the node FG (retaining)

Since the off-state current of the transistor 3300 is low, the charge of the node FG is retained for a long time.

Next, reading of data is described. An appropriate potential (a reading potential) is supplied to the fifth wiring 3005 while a predetermined potential (a constant potential) is supplied to the first wiring 3001, whereby the potential of the second wiring 3002 varies depending on the amount of charge retained in the node FG. This is because in the case of using an n-channel transistor as the transistor 3200, an apparent threshold voltage V_(th) _(_) _(H) at the time when the high-level charge is given to the gate of the transistor 3200 is lower than an apparent threshold voltage V_(th) _(_) _(L) at the time when the low-level charge is given to the gate of the transistor 3200. Here, an apparent threshold voltage refers to the potential of the fifth wiring 3005 which is needed to make the transistor 3200 be in “on state.” Thus, the potential of the fifth wiring 3005 is set to a potential V₀ which is between V_(th) _(_) _(H) and V_(th) _(_) _(L), whereby charge supplied to the node FG can be determined. For example, in the case where the high-level charge is supplied to the node FG in writing and the potential of the fifth wiring 3005 is V₀ (>V_(th) _(_) _(H)), the transistor 3200 is brought into “on state.” In the case where the low-level charge is supplied to the node FG in writing, even when the potential of the fifth wiring 3005 is V₀ (<V_(th) _(_) _(L)), the transistor 3200 still remains in “off state.” Thus, the data retained in the node FG can be read by determining the potential of the second wiring 3002.

Note that in the case where memory cells are arrayed, it is necessary that data of a desired memory cell be read in read operation. In the case where data of the other memory cells is not read, the fifth wiring 3005 may be supplied with a potential at which the transistor 3200 is in “off state” regardless of the charge supplied to the node FG, that is, a potential lower than V_(th) _(_) _(H). Alternatively, the fifth wiring 3005 may be supplied with a potential at which the transistor 3200 is brought into “on state” regardless of the charge supplied to the node FG, that is, a potential higher than V_(th) _(_) _(L).

<Structure 2 of Semiconductor Device>

FIG. 44 is a cross-sectional view of the semiconductor device of FIG. 43A. The semiconductor device shown in FIG. 44 includes the transistor 3200, the transistor 3300, and the capacitor 3400. The transistor 3300 and the capacitor 3400 are placed above the transistor 3200. Note that for the transistor 3300, the description of the above transistor 2100 is referred to. Furthermore, for the transistor 3200, the description of the transistor 2200 in FIG. 37 is referred to. Note that although the transistor 2200 is illustrated as a p-channel transistor in FIG. 37, the transistor 3200 may be an n-channel transistor.

The transistor 3200 illustrated in FIG. 44 is a transistor using a semiconductor substrate 450. The transistor 3200 includes a region 472 a in the semiconductor substrate 450, a region 472 b in the semiconductor substrate 450, an insulator 462, and a conductor 454.

The semiconductor device illustrated in FIG. 44 includes insulators 464, 466, and 468, conductors 480 a, 480 b, 480 c, 478 a, 478 b, 478 c, 476 a, 476 b, 474 a, 474 b, 474 c, 496 a, 496 b, 496 c, 496 d, 498 a, 498 b, 498 c, and 498 d, and insulators 490, 492, and 494.

The insulator 464 is provided over the transistor 3200. The insulator 466 is provided over the insulator 464. The insulator 468 is provided over the insulator 466. The insulator 490 is provided over the insulator 468. The transistor 3300 is provided over the insulator 490. The insulator 492 is provided over the transistor 3300. The insulator 494 is provided over the insulator 492.

The insulator 464 has an opening reaching the region 472 a, an opening reaching the region 472 b, and an opening reaching the conductor 454. In the openings, the conductor 480 a, the conductor 480 b, and the conductor 480 c are embedded.

The insulator 466 includes an opening reaching the conductor 480 a, an opening reaching the conductor 480 b, and an opening reaching the conductor 480 c. In the openings, the conductor 478 a, the conductor 478 b, and the conductor 478 c are embedded.

The insulator 468 includes an opening reaching the conductor 478 b and an opening reaching the conductor 478 c. In the openings, the conductor 476 a and the conductor 476 b are embedded.

The insulator 490 includes an opening overlapping the channel formation region of the transistor 3300, an opening reaching the conductor 476 a, and an opening reaching the conductor 476 b. In the openings, the conductors 474 a, the conductor 474 b, and the conductor 474 c are embedded.

The conductor 474 a may have a function as a bottom gate electrode of the transistor 3300. Alternatively, for example, electric characteristics such as the threshold voltage of the transistor 3300 may be controlled by application of a predetermined potential to the conductor 474 a. Further alternatively, for example, the conductor 474 a and the conductor 404 that is the top gate electrode of the transistor 3300 may be electrically connected to each other. Thus, the on-state current of the transistor 3300 can be increased. A punch-through phenomenon can be suppressed; thus, stable electric characteristics in the saturation region of the transistor 3300 can be obtained.

The insulator 492 includes an opening reaching the conductor 474 b through the conductor 516 b that is one of a source electrode and a drain electrode of the transistor 3300, an opening reaching the conductor 514 that overlaps the conductor 516 a that is the other of the source electrode and the drain electrode of the transistor 3300, with the insulator 511 positioned therebetween, an opening reaching the conductor 504 that is the gate electrode of the transistor 3300, and an opening reaching the conductor 474 c through the conductor 516 a that is the other of the source electrode and the drain electrode of the transistor 3300. In the openings, the conductor 496 a, the conductor 496 b, the conductor 496 c, and the conductor 496 d are embedded. Note that in some cases, a component of the transistor 3300 or the like is through other components.

The insulator 494 includes an opening reaching the conductor 496 a, an opening reaching the conductors 496 b, an opening reaching the conductor 496 c, and an opening reaching the conductor 496 d. In the openings, the conductors 498 a, 498 b, 498 c, and 498 d are embedded.

At least one of the insulators 464, 466, 468, 490, 492, and 494 preferably has a function of blocking oxygen and impurities such as hydrogen. When an insulator that has a function of blocking oxygen and impurities such as hydrogen is placed near the transistor 3300, the electrical characteristics of the transistor 3300 can be stable.

The conductor 498 d may be formed to have a single-layer structure or a stacked-layer structure including a conductor containing, for example, one or more kinds selected from boron, nitrogen, oxygen, fluorine, silicon, phosphorus, aluminum, titanium, chromium, manganese, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, molybdenum, ruthenium, silver, indium, tin, tantalum, and tungsten. An alloy or a compound of the above element may be used, for example, and a conductor containing aluminum, a conductor containing copper and titanium, a conductor containing copper and manganese, a conductor containing indium, tin, and oxygen, a conductor containing titanium and nitrogen, or the like may be used.

The source or drain of the transistor 3200 is electrically connected to the conductor 516 b that is one of a source electrode and a drain electrode of the transistor 3300 through the conductor 480 b, the conductor 478 b, the conductor 476 a, the conductor 474 b, and the conductor 496 c. The conductor 454 that is the gate electrode of the transistor 3200 is electrically connected to the conductor 516 a that is the other of the source electrode and the drain electrode of the transistor 3300 through the conductor 480 c, the conductor 478 c, the conductor 476 b, the conductor 474 c, and the conductor 496 d.

The capacitor 3400 includes an electrode electrically connected to the other of the source electrode and the drain electrode of the transistor 3300, the conductor 514, and an insulator 511. Because the insulator 511 can be formed by the same step as the insulator 512 that functions as a gate insulator of the transistor 3300, productivity can be increased. When a layer formed by the same step as the conductor 504 that functions as a gate electrode of the transistor 3300 is used as the conductor 514, productivity can be increased.

For the structures of other components, the description of FIG. 37 and the like can be referred to as appropriate.

A semiconductor device in FIG. 45 is the same as the semiconductor device in FIG. 44 except the structure of the transistor 3200. Therefore, the description of the semiconductor device in FIG. 44 is referred to for the semiconductor device in FIG. 45. Specifically, in the semiconductor device in FIG. 45, the transistor 3200 is a FIN-type transistor. For the FIN-type transistor 3200, the description of the transistor 2200 in FIG. 38 is referred to. Note that although the transistor 2200 is illustrated as a p-channel transistor in FIG. 38, the transistor 3200 may be an n-channel transistor.

A semiconductor device in FIG. 46 is the same as the semiconductor device in FIG. 44 except a structure of the transistor 3200. Therefore, the description of the semiconductor device in FIG. 44 is referred to for the semiconductor device in FIG. 46. Specifically, in the semiconductor device in FIG. 46, the transistor 3200 is provided in the semiconductor substrate 450 that is an SOI substrate. For the transistor 3200, which is provided in the semiconductor substrate 450 that is an SOI substrate, the description of the transistor 2200 in FIG. 39 is referred to. Note that although the transistor 2200 is illustrated as a p-channel transistor in FIG. 39, the transistor 3200 may be an n-channel transistor.

Semiconductor devices illustrated in FIG. 47, FIG. 48, and FIG. 49 are different from the semiconductor devices illustrated in FIG. 44, FIG. 45, and FIG. 46, respectively, only in the structure of the transistor 3300. The description of the transistor illustrated in FIGS. 14A and 14B can be referred to for the transistors 3300 illustrated in FIG. 47, FIG. 48, and FIG. 49, for example.

<Memory Device 2>

The semiconductor device in FIG. 43B is different from the semiconductor device in FIG. 43A in that the transistor 3200 is not provided. Also in this case, data can be written and retained in a manner similar to that of the semiconductor device in FIG. 43A.

Reading of data in the semiconductor device in FIG. 43B is described. When the transistor 3300 is brought into on state, the third wiring 3003 which is in a floating state and the capacitor 3400 are brought into conduction, and the charge is redistributed between the third wiring 3003 and the capacitor 3400. As a result, the potential of the third wiring 3003 is changed. The amount of change in the potential of the third wiring 3003 varies depending on the potential of the one electrode of the capacitor 3400 (or the charge accumulated in the capacitor 3400).

For example, the potential of the third wiring 3003 after the charge redistribution is (C_(B)×V_(B0)+C×V)/(C_(B)+C), where V is the potential of the one electrode of the capacitor 3400, C is the capacitance of the capacitor 3400, C_(B) is the capacitance component of the third wiring 3003, and V_(B0) is the potential of the third wiring 3003 before the charge redistribution. Thus, it can be found that, assuming that the memory cell is in either of two states in which the potential of the one electrode of the capacitor 3400 is V₁ and V₀ (V₁>V₀), the potential of the third wiring 3003 in the case of retaining the potential V₁ (=(C_(B)×V_(B0)+C×V₁)/(C_(B)+C)) is higher than the potential of the third wiring 3003 in the case of retaining the potential V₀ (=(C_(B)×V_(B0)+C×V₀)/(C_(B)±C)).

Then, by comparing the potential of the third wiring 3003 with a predetermined potential, data can be read.

In this case, a transistor including the first semiconductor may be used for a driver circuit for driving a memory cell, and a transistor including the second semiconductor may be stacked over the driver circuit as the transistor 3300.

When including a transistor using an oxide semiconductor and having a low off-state current, the semiconductor device described above can retain stored data for a long time. In other words, power consumption of the semiconductor device can be reduced because refresh operation becomes unnecessary or the frequency of refresh operation can be extremely low. Moreover, stored data can be retained for a long time even when power is not supplied (note that a potential is preferably fixed).

In the semiconductor device, high voltage is not needed for writing data and deterioration of elements is less likely to occur. Unlike in a conventional nonvolatile memory, for example, it is not necessary to inject and extract electrons into and from a floating gate; thus, a problem such as deterioration of an insulator is not caused. That is, the semiconductor device of one embodiment of the present invention does not have a limit on the number of times data can be rewritten, which is a problem of a conventional nonvolatile memory, and the reliability thereof is drastically improved. Furthermore, data is written depending on the on/off state of the transistor, whereby high-speed operation can be achieved.

<Imaging Device>

An imaging device of one embodiment of the present invention is described below.

FIG. 50A is a plan view illustrating an example of an imaging device 200 of one embodiment of the present invention. The imaging device 200 includes a pixel portion 210 and peripheral circuits for driving the pixel portion 210 (a peripheral circuit 260, a peripheral circuit 270, a peripheral circuit 280, and a peripheral circuit 290). The pixel portion 210 includes a plurality of pixels 211 arranged in a matrix with p rows and q columns (p and q are each a natural number greater than or equal to 2). The peripheral circuit 260, the peripheral circuit 270, the peripheral circuit 280, and the peripheral circuit 290 are each connected to a plurality of pixels 211, and a signal for driving the plurality of pixels 211 is supplied. In this specification and the like, in some cases, “a peripheral circuit” or “a driver circuit” indicates all of the peripheral circuits 260, 270, 280, and 290. For example, the peripheral circuit 260 can be regarded as part of the peripheral circuit.

The imaging device 200 preferably includes a light source 291. The light source 291 can emit detection light P1.

The peripheral circuit includes at least one of a logic circuit, a switch, a buffer, an amplifier circuit, and a converter circuit. The peripheral circuit may be provided over a substrate where the pixel portion 210 is formed. Part or the whole of the peripheral circuit may be mounted using a semiconductor device such as an IC. Note that as the peripheral circuit, one or more of the peripheral circuits 260, 270, 280, and 290 may be omitted.

As illustrated in FIG. 50B, the pixels 211 may be provided to be inclined in the pixel portion 210 included in the imaging device 200. When the pixels 211 are obliquely arranged, the distance between pixels (pitch) can be shortened in the row direction and the column direction. Accordingly, the quality of an image taken with the imaging device 200 can be improved.

<Configuration Example 1 of Pixel>

The pixel 211 included in the imaging device 200 is formed with a plurality of subpixels 212, and each subpixel 212 is combined with a filter which transmits light with a specific wavelength band (color filter), whereby data for achieving color image display can be obtained.

FIG. 51A is a plan view showing an example of the pixel 211 with which a color image is obtained. The pixel 211 illustrated in FIG. 51A includes a subpixel 212 provided with a color filter transmitting light with a red (R) wavelength band (also referred to as a subpixel 212R), a subpixel 212 provided with a color filter transmitting light with a green (G) wavelength band (also referred to as a subpixel 212G), and a subpixel 212 provided with a color filter transmitting light with a blue (B) wavelength band (also referred to as a subpixel 212B). The subpixel 212 can function as a photosensor.

The subpixel 212 (the subpixel 212R, the subpixel 212G, and the subpixel 212B) is electrically connected to a wiring 231, a wiring 247, a wiring 248, a wiring 249, and a wiring 250. In addition, the subpixel 212R, the subpixel 212G, and the subpixel 212B are connected to respective wirings 253 which are independent from one another. In this specification and the like, for example, the wiring 248 and the wiring 249 that are connected to the pixel 211 in the n-th row (n is an integer greater than or equal to 1 and less than or equal to p) are referred to as a wiring 248[n] and a wiring 249[n]. For example, the wiring 253 connected to the pixel 211 in the m-th column (m is an integer greater than or equal to 1 and less than or equal to q) is referred to as a wiring 253[m]. Note that in FIG. 51A, the wirings 253 connected to the subpixel 212R, the subpixel 212G, and the subpixel 212B in the pixel 211 in the m-th column are referred to as a wiring 253[m]R, a wiring 253[m]G, and a wiring 253[m]B. The subpixels 212 are electrically connected to the peripheral circuit through the above wirings.

The imaging device 200 has a structure in which the subpixel 212 is electrically connected to the subpixel 212 in an adjacent pixel 211 which is provided with a color filter transmitting light with the same wavelength band as the subpixel 212, via a switch. FIG. 51B shows a connection example of the subpixels 212: the subpixel 212 in the pixel 211 arranged in an n-th row and an m-th column and the subpixel 212 in the adjacent pixel 211 arranged in an (n+1)-th row and the m-th column. In FIG. 51B, the subpixel 212R arranged in the n-th row and the m-th column and the subpixel 212R arranged in the (n+1)-th row and the m-th column are connected to each other via a switch 201. The subpixel 212G arranged in the n-th row and the m-th column and the subpixel 212G arranged in the (n+1)-th row and the m-th column are connected to each other via a switch 202. The subpixel 212B arranged in the n-th row and the m-th column and the subpixel 212B arranged in the (n+1)-th row and the m-th column are connected to each other via a switch 203.

The color filter used in the subpixel 212 is not limited to red (R), green (G), and blue (B) color filters, and color filters that transmit light of cyan (C), yellow (Y), and magenta (M) may be used. By provision of the subpixels 212 that sense light with three different wavelength bands in one pixel 211, a full-color image can be obtained.

The pixel 211 including the subpixel 212 provided with a color filter transmitting yellow (Y) light may be provided, in addition to the subpixels 212 provided with the color filters transmitting red (R), green (G), and blue (B) light. The pixel 211 including the subpixel 212 provided with a color filter transmitting blue (B) light may be provided, in addition to the subpixels 212 provided with the color filters transmitting cyan (C), yellow (Y), and magenta (M) light. When the subpixels 212 sensing light with four different wavelength bands are provided in one pixel 211, the reproducibility of colors of an obtained image can be increased.

For example, in FIG. 51A, in regard to the subpixel 212 sensing a red wavelength band, the subpixel 212 sensing a green wavelength band, and the subpixel 212 sensing a blue wavelength band, the pixel number ratio (or the light receiving area ratio) thereof is not necessarily 1:1:1. For example, the Bayer arrangement in which the pixel number ratio (the light receiving area ratio) is set at red:green:blue=1:2:1 may be employed. Alternatively, the pixel number ratio (the light receiving area ratio) of red and green to blue may be 1:6:1.

Although the number of subpixels 212 provided in the pixel 211 may be one, two or more subpixels are preferably provided. For example, when two or more subpixels 212 sensing the same wavelength band are provided, the redundancy is increased, and the reliability of the imaging device 200 can be increased.

When an infrared (IR) filter that transmits infrared light and absorbs or reflects visible light is used as the filter, the imaging device 200 that senses infrared light can be achieved.

Furthermore, when a neutral density (ND) filter (dark filter) is used, output saturation which occurs when a large amount of light enters a photoelectric conversion element (light-receiving element) can be prevented. With a combination of ND filters with different dimming capabilities, the dynamic range of the imaging device can be increased.

Besides the above-described filter, the pixel 211 may be provided with a lens. An arrangement example of the pixel 211, a filter 254, and a lens 255 is described with cross-sectional views in FIGS. 52A and 52B. With the lens 255, the photoelectric conversion element can receive incident light efficiently. Specifically, as illustrated in FIG. 52A, light 256 enters a photoelectric conversion element 220 through the lens 255, the filter 254 (a filter 254R, a filter 254G, and a filter 254B), a pixel circuit 230, and the like which are provided in the pixel 211.

However, as indicated by a region surrounded with dashed-dotted lines, part of the light 256 indicated by arrows might be blocked by some wirings 257. Thus, a preferable structure is that the lens 255 and the filter 254 are provided on the photoelectric conversion element 220 side, so that the photoelectric conversion element 220 can efficiently receive the light 256 as illustrated in FIG. 52B. When the light 256 enters the photoelectric conversion element 220 from the photoelectric conversion element 220 side, the imaging device 200 with high sensitivity can be provided.

As the photoelectric conversion element 220 illustrated in FIGS. 52A and 52B, a photoelectric conversion element in which a p-n junction or a p-i-n junction is formed may be used.

The photoelectric conversion element 220 may be formed using a substance that has a function of absorbing a radiation and generating electric charges. Examples of the substance that has a function of absorbing a radiation and generating electric charges include selenium, lead iodide, mercury iodide, gallium arsenide, cadmium telluride, and cadmium zinc alloy.

For example, when selenium is used for the photoelectric conversion element 220, the photoelectric conversion element 220 can have a light absorption coefficient in a wide wavelength range, such as visible light, ultraviolet light, infrared light, X-rays, and gamma rays.

One pixel 211 included in the imaging device 200 may include the subpixel 212 with a first filter in addition to the subpixel 212 illustrated in FIGS. 51A and 51B.

<Configuration Example 2 of Pixel>

An example of a pixel including a transistor using silicon and a transistor using an oxide semiconductor is described below.

FIGS. 53A and 53B are each a cross-sectional view of an element included in an imaging device. The imaging device illustrated in FIG. 53A includes a transistor 351 including silicon over a silicon substrate 300, transistors 352 and 353 which include an oxide semiconductor and are stacked over the transistor 351, and a photodiode 360 provided in a silicon substrate 300. The transistors and the photodiode 360 are electrically connected to various plugs 370 and wirings 371. In addition, an anode 361 of the photodiode 360 is electrically connected to the plug 370 through a low-resistance region 363.

The imaging device includes a layer 310 including the transistor 351 provided on the silicon substrate 300 and the photodiode 360 provided in the silicon substrate 300, a layer 320 which is in contact with the layer 310 and includes the wirings 371, a layer 330 which is in contact with the layer 320 and includes the transistors 352 and 353, and a layer 340 which is in contact with the layer 330 and includes a wiring 372 and a wiring 373.

In the example of cross-sectional view in FIG. 53A, a light-receiving surface of the photodiode 360 is provided on the side opposite to a surface of the silicon substrate 300 where the transistor 351 is formed. With this structure, a light path can be secured without an influence of the transistors and the wirings. Thus, a pixel with a high aperture ratio can be formed. Note that the light-receiving surface of the photodiode 360 can be the same as the surface where the transistor 351 is formed.

In the case where a pixel is formed with use of transistors using an oxide semiconductor, the layer 310 may include the transistor using an oxide semiconductor. Alternatively, the layer 310 may be omitted, and the pixel may include only transistors using an oxide semiconductor.

In the case where a pixel is formed with use of transistors using silicon, the layer 330 may be omitted. An example of a cross-sectional view in which the layer 330 is not provided is shown in FIG. 53B. In the case where the layer 330 is not provided, the wiring 372 of the layer 340 can be omitted.

Note that the silicon substrate 300 may be an SOI substrate. Furthermore, the silicon substrate 300 can be replaced with a substrate made of germanium, silicon germanium, silicon carbide, gallium arsenide, aluminum gallium arsenide, indium phosphide, gallium nitride, or an organic semiconductor.

Here, an insulator 380 is provided between the layer 310 including the transistor 351 and the photodiode 360 and the layer 330 including the transistors 352 and 353. However, there is no limitation on the position of the insulator 380.

Hydrogen in an insulator provided in the vicinity of a channel formation region of the transistor 351 terminates dangling bonds of silicon; accordingly, the reliability of the transistor 351 can be improved. In contrast, hydrogen in the insulator provided in the vicinity of the transistor 352, the transistor 353, and the like becomes one of factors generating a carrier in the oxide semiconductor. Thus, the hydrogen may cause a reduction of the reliability of the transistor 352, the transistor 353, and the like. Therefore, in the case where the transistor using an oxide semiconductor is provided over the transistor using a silicon-based semiconductor, it is preferable that the insulator 380 having a function of blocking hydrogen be provided between the transistors. When the hydrogen is confined below the insulator 380, the reliability of the transistor 351 can be improved. In addition, the hydrogen can be prevented from being diffused from a part below the insulator 380 to a part above the insulator 380; thus, the reliability of the transistor 352, the transistor 353, and the like can be increased.

As the insulator 380, an insulator having a function of blocking oxygen or hydrogen is used, for example.

In the cross-sectional view in FIG. 53A, the photodiode 360 in the layer 310 and the transistor in the layer 330 can be formed so as to overlap each other. Thus, the degree of integration of pixels can be increased. In other words, the resolution of the imaging device can be increased.

As illustrated in FIG. 54A1 and FIG. 54B1, part or the whole of the imaging device can be bent. FIG. 54A1 illustrates a state in which the imaging device is bent in the direction of a dashed-dotted line X1-X2. FIG. 54A2 is a cross-sectional view illustrating a portion indicated by the dashed-dotted line X1-X2 in FIG. 54A1. FIG. 54A3 is a cross-sectional view illustrating a portion indicated by a dashed-dotted line Y1-Y2 in FIG. 54A1.

FIG. 54B1 illustrates a state where the imaging device is bent in the direction of a dashed-dotted chain X3-X4 and the direction of a dashed-dotted line Y3-Y4. FIG. 54B2 is a cross-sectional view illustrating a portion indicated by the dashed-dotted line X3-X4 in FIG. 54B1. FIG. 54B3 is a cross-sectional view illustrating a portion indicated by the dashed-dotted line Y3-Y4 in FIG. 54B1.

The bent imaging device enables the curvature of field and astigmatism to be reduced. Thus, the optical design of lens and the like, which is used in combination of the imaging device, can be facilitated. For example, the number of lens used for aberration correction can be reduced; accordingly, a reduction of size or weight of electronic devices using the imaging device, and the like, can be achieved. In addition, the quality of a captured image can be improved.

<CPU>

A CPU including a semiconductor device such as any of the above-described transistors or the above-described memory device is described below.

FIG. 55 is a block diagram illustrating a configuration example of a CPU including any of the above-described transistors as a component.

The CPU illustrated in FIG. 55 includes, over a substrate 1190, an arithmetic logic unit (ALU) 1191, an ALU controller 1192, an instruction decoder 1193, an interrupt controller 1194, a timing controller 1195, a register 1196, a register controller 1197, a bus interface 1198, a rewritable ROM 1199, and a ROM interface 1189. A semiconductor substrate, an SOI substrate, a glass substrate, or the like is used as the substrate 1190. The ROM 1199 and the ROM interface 1189 may be provided over a separate chip. Needless to say, the CPU in FIG. 55 is just an example in which the configuration has been simplified, and an actual CPU may have a variety of configurations depending on the application. For example, the CPU may have the following configuration: a structure including the CPU illustrated in FIG. 55 or an arithmetic circuit is considered as one core; a plurality of such cores are included; and the cores operate in parallel. The number of bits that the CPU can process in an internal arithmetic circuit or in a data bus can be 8, 16, 32, or 64, for example.

An instruction that is input to the CPU through the bus interface 1198 is input to the instruction decoder 1193 and decoded therein, and then, input to the ALU controller 1192, the interrupt controller 1194, the register controller 1197, and the timing controller 1195.

The ALU controller 1192, the interrupt controller 1194, the register controller 1197, and the timing controller 1195 conduct various controls in accordance with the decoded instruction. Specifically, the ALU controller 1192 generates signals for controlling the operation of the ALU 1191. While the CPU is executing a program, the interrupt controller 1194 judges an interrupt request from an external input/output device or a peripheral circuit on the basis of its priority or a mask state, and processes the request. The register controller 1197 generates an address of the register 1196, and reads/writes data from/to the register 1196 in accordance with the state of the CPU.

The timing controller 1195 generates signals for controlling operation timings of the ALU 1191, the ALU controller 1192, the instruction decoder 1193, the interrupt controller 1194, and the register controller 1197. For example, the timing controller 1195 includes an internal clock generator for generating an internal clock signal based on a reference clock signal, and supplies the internal clock signal to the above circuits.

In the CPU illustrated in FIG. 55, a memory cell is provided in the register 1196. For the memory cell of the register 1196, any of the above-described transistors, the above-described memory device, or the like can be used.

In the CPU illustrated in FIG. 55, the register controller 1197 selects operation of retaining data in the register 1196 in accordance with an instruction from the ALU 1191. That is, the register controller 1197 selects whether data is retained by a flip-flop or by a capacitor in the memory cell included in the register 1196. When data retention by the flip-flop is selected, a power supply voltage is supplied to the memory cell in the register 1196. When data retention by the capacitor is selected, the data is rewritten in the capacitor, and supply of a power supply voltage to the memory cell in the register 1196 can be stopped.

FIG. 56 is an example of a circuit diagram of a memory element 1200 that can be used as the register 1196. The memory element 1200 includes a circuit 1201 in which stored data is volatile when power supply is stopped, a circuit 1202 in which stored data is nonvolatile even when power supply is stopped, a switch 1203, a switch 1204, a logic element 1206, a capacitor 1207, and a circuit 1220 having a selecting function. The circuit 1202 includes a capacitor 1208, a transistor 1209, and a transistor 1210. Note that the memory element 1200 may further include another element such as a diode, a resistor, or an inductor, as needed.

Here, the above-described memory device can be used as the circuit 1202. When supply of a power supply voltage to the memory element 1200 is stopped, GND (0 V) or a potential at which the transistor 1209 in the circuit 1202 is turned off continues to be input to a gate of the transistor 1209. For example, the gate of the transistor 1209 is grounded through a load such as a resistor.

Shown here is an example in which the switch 1203 is a transistor 1213 having one conductivity type (e.g., an n-channel transistor) and the switch 1204 is a transistor 1214 having a conductivity type opposite to the one conductivity type (e.g., a p-channel transistor). A first terminal of the switch 1203 corresponds to one of a source and a drain of the transistor 1213, a second terminal of the switch 1203 corresponds to the other of the source and the drain of the transistor 1213, and conduction or non-conduction between the first terminal and the second terminal of the switch 1203 (i.e., the on/off state of the transistor 1213) is selected by a control signal RD input to a gate of the transistor 1213. A first terminal of the switch 1204 corresponds to one of a source and a drain of the transistor 1214, a second terminal of the switch 1204 corresponds to the other of the source and the drain of the transistor 1214, and conduction or non-conduction between the first terminal and the second terminal of the switch 1204 (i.e., the on/off state of the transistor 1214) is selected by the control signal RD input to a gate of the transistor 1214.

One of a source and a drain of the transistor 1209 is electrically connected to one of a pair of electrodes of the capacitor 1208 and a gate of the transistor 1210. Here, the connection portion is referred to as a node M2. One of a source and a drain of the transistor 1210 is electrically connected to a line which can supply a low power supply potential (e.g., a GND line), and the other thereof is electrically connected to the first terminal of the switch 1203 (the one of the source and the drain of the transistor 1213). The second terminal of the switch 1203 (the other of the source and the drain of the transistor 1213) is electrically connected to the first terminal of the switch 1204 (the one of the source and the drain of the transistor 1214). The second terminal of the switch 1204 (the other of the source and the drain of the transistor 1214) is electrically connected to a line which can supply a power supply potential VDD. The second terminal of the switch 1203 (the other of the source and the drain of the transistor 1213), the first terminal of the switch 1204 (the one of the source and the drain of the transistor 1214), an input terminal of the logic element 1206, and one of a pair of electrodes of the capacitor 1207 are electrically connected to each other. Here, the connection portion is referred to as a node M1. The other of the pair of electrodes of the capacitor 1207 can be supplied with a constant potential. For example, the other of the pair of electrodes of the capacitor 1207 can be supplied with a low power supply potential (e.g., GND) or a high power supply potential (e.g., VDD). The other of the pair of electrodes of the capacitor 1207 is electrically connected to the line which can supply a low power supply potential (e.g., a GND line). The other of the pair of electrodes of the capacitor 1208 can be supplied with a constant potential. For example, the other of the pair of electrodes of the capacitor 1208 can be supplied with the low power supply potential (e.g., GND) or the high power supply potential (e.g., VDD). The other of the pair of electrodes of the capacitor 1208 is electrically connected to the line which can supply a low power supply potential (e.g., a GND line).

The capacitor 1207 and the capacitor 1208 are not necessarily provided as long as the parasitic capacitance of the transistor, the wiring, or the like is actively utilized.

A control signal WE is input to the gate of the transistor 1209. As for each of the switch 1203 and the switch 1204, a conduction state or a non-conduction state between the first terminal and the second terminal is selected by the control signal RD which is different from the control signal WE. When the first terminal and the second terminal of one of the switches are in the conduction state, the first terminal and the second terminal of the other of the switches are in the non-conduction state.

A signal corresponding to data retained in the circuit 1201 is input to the other of the source and the drain of the transistor 1209. FIG. 56 illustrates an example in which a signal output from the circuit 1201 is input to the other of the source and the drain of the transistor 1209. The logic value of a signal output from the second terminal of the switch 1203 (the other of the source and the drain of the transistor 1213) is inverted by the logic element 1206, and the inverted signal is input to the circuit 1201 through the circuit 1220.

In the example of FIG. 56, a signal output from the second terminal of the switch 1203 (the other of the source and the drain of the transistor 1213) is input to the circuit 1201 through the logic element 1206 and the circuit 1220; however, one embodiment of the present invention is not limited thereto. The signal output from the second terminal of the switch 1203 (the other of the source and the drain of the transistor 1213) may be input to the circuit 1201 without its logic value being inverted. For example, in the case where the circuit 1201 includes a node in which a signal obtained by inversion of the logic value of a signal input from the input terminal is retained, the signal output from the second terminal of the switch 1203 (the other of the source and the drain of the transistor 1213) can be input to the node.

In FIG. 56, the transistors included in the memory element 1200 except for the transistor 1209 can each be a transistor in which a channel is formed in a film formed using a semiconductor other than an oxide semiconductor or in the substrate 1190. For example, the transistor can be a transistor whose channel is formed in a silicon film or a silicon substrate. Alternatively, all the transistors in the memory element 1200 may be a transistor in which a channel is formed in an oxide semiconductor. Further alternatively, in the memory element 1200, a transistor in which a channel is formed in an oxide semiconductor may be included besides the transistor 1209, and a transistor in which a channel is formed in a film formed using a semiconductor other than an oxide semiconductor or in the substrate 1190 can be used for the rest of the transistors.

As the circuit 1201 in FIG. 56, for example, a flip-flop circuit can be used. As the logic element 1206, for example, an inverter or a clocked inverter can be used.

In a period during which the memory element 1200 is not supplied with the power supply voltage, the semiconductor device of one embodiment of the present invention can retain data stored in the circuit 1201 by the capacitor 1208 which is provided in the circuit 1202.

The off-state current of a transistor in which a channel is formed in an oxide semiconductor is extremely low. For example, the off-state current of a transistor in which a channel is formed in an oxide semiconductor is significantly lower than that of a transistor in which a channel is formed in silicon having crystallinity. Thus, when the transistor is used as the transistor 1209, a signal held in the capacitor 1208 is retained for a long time also in a period during which the power supply voltage is not supplied to the memory element 1200. The memory element 1200 can accordingly retain the stored content (data) also in a period during which the supply of the power supply voltage is stopped.

Since the above-described memory element performs pre-charge operation with the switch 1203 and the switch 1204, the time required for the circuit 1201 to retain original data again after the supply of the power supply voltage is restarted can be shortened.

In the circuit 1202, a signal retained by the capacitor 1208 is input to the gate of the transistor 1210. Therefore, after supply of the power supply voltage to the memory element 1200 is restarted, the transistor 1210 is turned on or turned off depending on the signal retained by the capacitor 1208, and a signal corresponding to the state can be read from the circuit 1202. Consequently, an original signal can be accurately read even when a potential corresponding to the signal retained by the capacitor 1208 varies to some degree.

By applying the above-described memory element 1200 to a memory device such as a register or a cache memory included in a processor, data in the memory device can be prevented from being lost owing to the stop of the supply of the power supply voltage. Furthermore, shortly after the supply of the power supply voltage is restarted, the memory device can be returned to the same state as that before the power supply is stopped. Therefore, the power supply can be stopped even for a short time in the processor or one or a plurality of logic circuits included in the processor, resulting in lower power consumption.

Although the memory element 1200 is used in a CPU, the memory element 1200 can also be used in an LSI such as a digital signal processor (DSP), a custom LSI, or a programmable logic device (PLD), and a radio frequency (RF) device.

<Display Device>

A display device of one embodiment of the present invention is described below with reference to FIGS. 57A to 57C and FIGS. 58A and 58B.

Examples of a display element provided in the display device include a liquid crystal element (also referred to as a liquid crystal display element) and a light-emitting element (also referred to as a light-emitting display element). The light-emitting element includes, in its category, an element whose luminance is controlled by a current or voltage, and specifically includes, in its category, an inorganic electroluminescent (EL) element, an organic EL element, and the like. A display device including an EL element (EL display device) and a display device including a liquid crystal element (liquid crystal display device) are described below as examples of the display device.

Note that the display device described below includes in its category a panel in which a display element is sealed and a module in which an IC such as a controller is mounted on the panel.

The display device described below refers to an image display device or a light source (including a lighting device). The display device includes any of the following modules: a module provided with a connector such as an FPC or TCP; a module in which a printed wiring board is provided at the end of TCP; and a module in which an integrated circuit (IC) is mounted directly on a display element by a COG method.

FIGS. 57A to 57C illustrate an example of an EL display device of one embodiment of the present invention. FIG. 57A is a circuit diagram of a pixel in an EL display device. FIG. 57B is a plan view showing the whole of the EL display device.

FIG. 57A illustrates an example of a circuit diagram of a pixel used in an EL display device.

Note that in this specification and the like, it might be possible for those skilled in the art to constitute one embodiment of the invention even when portions to which all the terminals of an active element (e.g., a transistor or a diode), a passive element (e.g., a capacitor or a resistor), or the like are connected are not specified. In other words, one embodiment of the invention can be clear even when connection portions are not specified. Further, in the case where a connection portion is disclosed in this specification and the like, it can be determined that one embodiment of the invention in which a connection portion is not specified is disclosed in this specification and the like, in some cases. Particularly in the case where the number of portions to which a terminal is connected might be more than one, it is not necessary to specify the portions to which the terminal is connected. Therefore, it might be possible to constitute one embodiment of the invention by specifying only portions to which some of terminals of an active element (e.g., a transistor or a diode), a passive element (e.g., a capacitor or a resistor), or the like are connected.

Note that in this specification and the like, it might be possible for those skilled in the art to specify the invention when at least the connection portion of a circuit is specified. Alternatively, it might be possible for those skilled in the art to specify the invention when at least a function of a circuit is specified. In other words, when a function of a circuit is specified, one embodiment of the present invention can be clear. Further, it can be determined that one embodiment of the present invention whose function is specified is disclosed in this specification and the like. Therefore, when a connection portion of a circuit is specified, the circuit is disclosed as one embodiment of the invention even when a function is not specified, and one embodiment of the invention can be constituted. Alternatively, when a function of a circuit is specified, the circuit is disclosed as one embodiment of the invention even when a connection portion is not specified, and one embodiment of the invention can be constituted.

The EL display device illustrated in FIG. 57A includes a switching element 743, a transistor 741, a capacitor 742, and a light-emitting element 719.

Note that FIG. 57A and the like each illustrate an example of a circuit structure; therefore, a transistor can be provided additionally. In contrast, for each node in FIG. 57A and the like, it is possible not to provide an additional transistor, switch, passive element, or the like.

A gate of the transistor 741 is electrically connected to one terminal of the switching element 743 and one electrode of the capacitor 742. A source of the transistor 741 is electrically connected to the other electrode of the capacitor 742 and one electrode of the light-emitting element 719. A drain of the transistor 741 is supplied with a power supply potential VDD. The other terminal of the switching element 743 is electrically connected to a signal line 744. A constant potential is supplied to the other electrode of the light-emitting element 719. The constant potential is a ground potential GND or a potential lower than the ground potential GND.

It is preferable to use a transistor as the switching element 743. When the transistor is used as the switching element, the area of a pixel can be reduced, so that the EL display device can have high resolution. As the switching element 743, a transistor formed through the same step as the transistor 741 can be used, so that EL display devices can be manufactured with high productivity. Note that as the transistor 741 and/or the switching element 743, any of the above-described transistors can be used, for example.

FIG. 57B is a plan view of the EL display device. The EL display device includes a substrate 700, a substrate 750, a sealant 734, a driver circuit 735, a driver circuit 736, a pixel 737, and an FPC 732. The sealant 734 is provided between the substrate 700 and the substrate 750 so as to surround the pixel 737, the driver circuit 735, and the driver circuit 736. Note that the driver circuit 735 and/or the driver circuit 736 may be provided outside the sealant 734.

FIG. 57C is a cross-sectional view of the EL display device taken along part of dashed-dotted line M-N in FIG. 57B.

FIG. 57C illustrates a structure of the transistor 741 including a conductor 704 a over the substrate 700; an insulator 712 a over the conductor 704 a; an insulator 712 b over the insulator 712 a; a semiconductor 706 a and a semiconductor 706 b which are over the insulator 712 b and overlaps the conductor 704 a; a conductor 716 a and a conductor 716 b in contact with the semiconductors 706 a and 706 b; an insulator 718 a over the semiconductor 706 b, the conductor 716 a, and the conductor 716 b; an insulator 718 b over the insulator 718 a; an insulator 718 c over the insulator 718 b; and a conductor 714 a that is over the insulator 718 c and overlaps the semiconductor 706 b. Note that the structure of the transistor 741 is just an example; the transistor 741 may have a structure different from that illustrated in FIG. 57C.

Thus, in the transistor 741 illustrated in FIG. 57C, the conductor 704 a serves as a gate electrode, the insulator 712 a and the insulator 712 b serve as a gate insulator, the conductor 716 a serves as a source electrode, the conductor 716 b serves as a drain electrode, the insulator 718 a, the insulator 718 b, and the insulator 718 c serve as a gate insulator, and the conductor 714 a serves as a gate electrode. Note that in some cases, electrical characteristics of the semiconductors 706 a and 706 b change if light enters the semiconductor. To prevent this, it is preferable that one or more of the conductor 704 a, the conductor 716 a, the conductor 716 b, and the conductor 714 a have a light-blocking property.

Note that the interface between the insulator 718 a and the insulator 718 b is indicated by a broken line. This means that the boundary between them is not clear in some cases. For example, in the case where the insulator 718 a and the insulator 718 b are formed using insulators of the same kind, the insulator 718 a and the insulator 718 b are not distinguished from each other in some cases depending on an observation method.

FIG. 57C illustrates a structure of the capacitor 742 including a conductor 704 b over the substrate; the insulator 712 a over the conductor 704 b; the insulator 712 b over the insulator 712 a; the conductor 716 a that is over the insulator 712 b and overlaps the conductor 704 b; the insulator 718 a over the conductor 716 a; the insulator 718 b over the insulator 718 a; the insulator 718 c over the insulator 718 b; and a conductor 714 b that is over the insulator 718 c and overlaps the conductor 716 a. In this structure, part of the insulator 718 a and part of the insulator 718 b are removed in a region where the conductor 716 a and the conductor 714 b overlap each other.

In the capacitor 742, each of the conductor 704 b and the conductor 714 b serves as one electrode, and the conductor 716 a serves as the other electrode.

Thus, the capacitor 742 can be formed using a film of the transistor 741. The conductor 704 a and the conductor 704 b are preferably conductors of the same kind, in which case the conductor 704 a and the conductor 704 b can be formed through the same step. Furthermore, the conductor 714 a and the conductor 714 b are preferably conductors of the same kind, in which case the conductor 714 a and the conductor 714 b can be formed through the same step.

The capacitor 742 illustrated in FIG. 57C has a large capacitance per area occupied by the capacitor. Therefore, the EL display device illustrated in FIG. 57C has high display quality. Note that although the capacitor 742 illustrated in FIG. 57C has the structure in which the part of the insulator 718 a and the part of the insulator 718 b are removed to reduce the thickness of the region where the conductor 716 a and the conductor 714 b overlap with each other, the structure of the capacitor according to one embodiment of the present invention is not limited to the structure. For example, a structure in which a part of the insulator 718 c is removed to reduce the thickness of the region where the conductor 716 a and the conductor 714 b overlap with each other may be used.

An insulator 720 is provided over the transistor 741 and the capacitor 742. Here, the insulator 720 may have an opening portion reaching the conductor 716 a that serves as the source electrode of the transistor 741. A conductor 781 is provided over the insulator 720. The conductor 781 may be electrically connected to the transistor 741 through the opening portion in the insulator 720.

A partition wall 784 having an opening portion reaching the conductor 781 is provided over the conductor 781. A light-emitting layer 782 in contact with the conductor 781 through the opening portion provided in the partition wall 784 is provided over the partition wall 784. A conductor 783 is provided over the light-emitting layer 782. A region where the conductor 781, the light-emitting layer 782, and the conductor 783 overlap with one another serves as the light-emitting element 719.

So far, examples of the EL display device are described. Next, an example of a liquid crystal display device is described.

FIG. 58A is a circuit diagram illustrating a configuration example of a pixel of a liquid crystal display device. A pixel shown in FIGS. 58A and 58B includes a transistor 751, a capacitor 752, and an element (liquid crystal element) 753 in which a space between a pair of electrodes is filled with a liquid crystal.

One of a source and a drain of the transistor 751 is electrically connected to a signal line 755, and a gate of the transistor 751 is electrically connected to a scan line 754.

One electrode of the capacitor 752 is electrically connected to the other of the source and the drain of the transistor 751, and the other electrode of the capacitor 752 is electrically connected to a wiring for supplying a common potential.

One electrode of the liquid crystal element 753 is electrically connected to the other of the source and the drain of the transistor 751, and the other electrode of the liquid crystal element 753 is electrically connected to a wiring to which a common potential is supplied. The common potential supplied to the wiring electrically connected to the other electrode of the capacitor 752 may be different from that supplied to the other electrode of the liquid crystal element 753.

Note that the description of the liquid crystal display device is made on the assumption that the plan view of the liquid crystal display device is similar to that of the EL display device. FIG. 58B is a cross-sectional view of the liquid crystal display device taken along dashed-dotted line M-N in FIG. 57B. In FIG. 58B, the FPC 732 is connected to the wiring 733 a via the terminal 731. Note that the wiring 733 a may be formed using the same kind of conductor as the conductor of the transistor 751 or using the same kind of semiconductor as the semiconductor of the transistor 751.

For the transistor 751, the description of the transistor 741 is referred to. For the capacitor 752, the description of the capacitor 742 is referred to. Note that the structure of the capacitor 752 in FIG. 58B corresponds to, but is not limited to, the structure of the capacitor 742 in FIG. 57C.

Note that in the case where an oxide semiconductor is used as the semiconductor of the transistor 751, the off-state current of the transistor 751 can be extremely small. Therefore, an electric charge held in the capacitor 752 is unlikely to leak, so that the voltage applied to the liquid crystal element 753 can be maintained for a long time. Accordingly, the transistor 751 can be kept off during a period in which moving images with few motions or a still image are/is displayed, whereby power for the operation of the transistor 751 can be saved in that period; accordingly a liquid crystal display device with low power consumption can be provided. Furthermore, the area occupied by the capacitor 752 can be reduced; thus, a liquid crystal display device with a high aperture ratio or a high-resolution liquid crystal display device can be provided.

An insulator 721 is provided over the transistor 751 and the capacitor 752. The insulator 721 has an opening portion reaching the transistor 751. A conductor 791 is provided over the insulator 721. The conductor 791 is electrically connected to the transistor 751 through the opening portion in the insulator 721.

An insulator 792 serving as an alignment film is provided over the conductor 791. A liquid crystal layer 793 is provided over the insulator 792. An insulator 794 serving as an alignment film is provided over the liquid crystal layer 793. A spacer 795 is provided over the insulator 794. A conductor 796 is provided over the spacer 795 and the insulator 794. A substrate 797 is provided over the conductor 796.

Owing to the above-described structure, a display device including a capacitor occupying a small area, a display device with high display quality, or a high-resolution display device can be provided.

For example, in this specification and the like, a display element, a display device which is a device including a display element, a light-emitting element, and a light-emitting device which is a device including a light-emitting element can employ various modes or can include various elements. For example, the display element, the display device, the light-emitting element, or the light-emitting device includes at least one of an EL element (e.g., an EL element including organic and inorganic materials, an organic EL element, or an inorganic EL element), a light-emitting diode (LED) for white, red, green, blue, or the like, a transistor (a transistor that emits light depending on current), an electron emitter, a liquid crystal element, electronic ink, an electrophoretic element, a grating light valve (GLV), a plasma display panel (PDP), a display element using micro electro mechanical systems (MEMS), a digital micromirror device (DMD), a digital micro shutter (DMS), an interferometric modulator display (IMOD) element, a MEMS shutter display element, an optical-interference-type MEMS display element, an electrowetting element, a piezoelectric ceramic display, and a display element including a carbon nanotube. Other than the above, display media whose contrast, luminance, reflectivity, transmittance, or the like is changed by electrical or magnetic effect may be included.

Note that examples of display devices having EL elements include an EL display. Examples of a display device including an electron emitter include a field emission display (FED), an SED-type flat panel display (SED: surface-conduction electron-emitter display), and the like. Examples of display devices including liquid crystal elements include a liquid crystal display (e.g., a transmissive liquid crystal display, a transflective liquid crystal display, a reflective liquid crystal display, a direct-view liquid crystal display, or a projection liquid crystal display). Examples of a display device having electronic ink or an electrophoretic element include electronic paper. In the case of a transflective liquid crystal display or a reflective liquid crystal display, some of or all of pixel electrodes function as reflective electrodes. For example, some or all of pixel electrodes are formed to contain aluminum, silver, or the like. In such a case, a memory circuit such as an SRAM can be provided under the reflective electrodes. Thus, the power consumption can be further reduced.

Note that in the case of using an LED, graphene or graphite may be provided under an electrode or a nitride semiconductor of the LED. Graphene or graphite may be a multilayer film in which a plurality of layers are stacked. As described above, provision of graphene or graphite enables easy formation of a nitride semiconductor thereover, such as an n-type GaN semiconductor including crystals. Furthermore, a p-type GaN semiconductor including crystals or the like can be provided thereover, and thus the LED can be formed. Note that an MN layer may be provided between the n-type GaN semiconductor including crystals and graphene or graphite. The GaN semiconductors included in the LED may be formed by MOCVD. Note that when the graphene is provided, the GaN semiconductors included in the LED can also be formed by a sputtering method.

<Electronic Device>

The semiconductor device of one embodiment of the present invention can be used for display devices, personal computers, or image reproducing devices provided with recording media (typically, devices which reproduce the content of recording media such as digital versatile discs (DVDs) and have displays for displaying the reproduced images). Other examples of electronic devices that can be equipped with the semiconductor device of one embodiment of the present invention are mobile phones, game machines including portable game consoles, portable data terminals, e-book readers, cameras such as video cameras and digital still cameras, goggle-type displays (head mounted displays), navigation systems, audio reproducing devices (e.g., car audio systems and digital audio players), copiers, facsimiles, printers, multifunction printers, automated teller machines (ATM), and vending machines. FIGS. 59A to 59F illustrate specific examples of these electronic devices.

FIG. 59A illustrates a portable game console including a housing 901, a housing 902, a display portion 903, a display portion 904, a microphone 905, a speaker 906, an operation key 907, a stylus 908, and the like. Although the portable game console in FIG. 59A has the two display portions 903 and 904, the number of display portions included in a portable game console is not limited to this.

FIG. 59B illustrates a portable data terminal including a first housing 911, a second housing 912, a first display portion 913, a second display portion 914, a joint 915, an operation key 916, and the like. The first display portion 913 is provided in the first housing 911, and the second display portion 914 is provided in the second housing 912. The first housing 911 and the second housing 912 are connected to each other with the joint 915, and the angle between the first housing 911 and the second housing 912 can be changed with the joint 915. An image on the first display portion 913 may be switched in accordance with the angle at the joint 915 between the first housing 911 and the second housing 912. A display device with a position input function may be used as at least one of the first display portion 913 and the second display portion 914. Note that the position input function can be added by providing a touch panel in a display device. Alternatively, the position input function can be added by providing a photoelectric conversion element called a photosensor in a pixel portion of a display device.

FIG. 59C illustrates a laptop personal computer, which includes a housing 921, a display portion 922, a keyboard 923, a pointing device 924, and the like.

FIG. 59D illustrates an electric refrigerator-freezer, which includes a housing 931, a door for a refrigerator 932, a door for a freezer 933, and the like.

FIG. 59E illustrates a video camera, which includes a first housing 941, a second housing 942, a display portion 943, operation keys 944, a lens 945, a joint 946, and the like. The operation keys 944 and the lens 945 are provided for the first housing 941, and the display portion 943 is provided for the second housing 942. The first housing 941 and the second housing 942 are connected to each other with the joint 946, and the angle between the first housing 941 and the second housing 942 can be changed with the joint 946. Images displayed on the display portion 943 may be switched in accordance with the angle at the joint 946 between the first housing 941 and the second housing 942.

FIG. 59F illustrates a car including a car body 951, wheels 952, a dashboard 953, lights 954, and the like.

Embodiments of the present invention are described above. Note that one embodiment of the present invention is not limited to the above description. For example, an example where an insulator such as the insulator 402 includes fluorine or hydrogen is described, but one embodiment of the present invention is not limited thereto. Depending on circumstances, the insulator such as the insulator 402 may include an element other than fluorine or an element other than hydrogen; alternatively, the insulator such as the insulator 402 does not necessarily include fluorine or hydrogen.

Example 1

In this example, it was verified whether excess oxygen is formed by adding fluorine to a silicon oxide.

A sample was fabricated in such a manner that a 100-nm-thick silicon oxide film was formed over a silicon substrate by a thermal oxidation method.

By an ion implantation method, ¹⁹F⁺ ions with a dose of 1.0×10¹⁶ ions/cm² was added to the sample. Note that the accelerating voltage was 10 kV. FIG. 69 shows the calculation value of the amount of added fluorine in the depth direction. FIG. 69 also shows the amounts of added fluorine in the depth direction with accelerating voltages of 15 kV and 20 kV as reference values. For the calculation, SRIM, the Stopping and Range of Ions in Matter, was used. The silicon oxide here had two oxygen atoms with respect to one silicon atom. The density of the silicon oxide was 2.2 g/cm³.

FIG. 70 shows changes in fluorine concentration in the depth direction of a sample to which fluorine was added (referred to as Example Sample) and a sample which was fabricated for comparison and to which fluorine was not added (referred to as Comparative Sample 1). A dashed line in FIG. 70 indicates a lower limit of this measurement. The fluorine concentration was measured with a PHI ADEPT-1010 quadrupole SIMS instrument manufactured by ULVAC-PHI, Incorporated. By comparison of FIG. 69 with FIG. 70, it is found that fluorine was added substantially as calculated.

Next, TDS analysis was performed in a sample surface temperature ranging approximately from 50° C. to 500° C. A thermal desorption spectroscopy apparatus EMD-WA1000S/W manufactured by ESCO Ltd. was used for the TDS analysis. Here, a sample was fabricated in such a manner that ⁴⁰Ar⁺ ions with a dose of 1.0×10¹⁶ ions/cm² was added by an ion implantation method (referred to as Comparative Example 2), and subjected to the above described analysis.

FIG. 71 shows the amount of a released gas having a mass-to-charge ratio of 19 (e.g., F) and the amount of a released gas having a mass-to-charge ratio of 32 (e.g., O₂). The results indicate that the amount of a released gas having a mass-to-charge ratio of 32 in Example Sample increased as compared with that in the samples to which fluorine was not added (Comparative Sample 1 and Comparative Sample 2). Specifically, the amount of oxygen molecules released from Example Sample was 2.1×10¹⁵ molecules/cm². This indicates that excess oxygen was formed in the silicon oxide by addition of fluorine. In Example Sample, the amount of the released gas having a mass-to-charge ratio of 19 also increased.

Next, unpaired electrons included in Example Sample and Comparative Sample 1 were measured by ESR. For the ESR measurement, an electron spin resonance spectrometer JES-FA300 manufactured by JEOL Ltd. was used, the temperature was set to 10 K, microwave power (9.56 GHz) was set to 0.1 mW, and the samples were placed such that the direction of a magnetic field was parallel to the surface of the substrate. As each sample, two rectangular silicon oxides with a size of 2 mm×10 mm were prepared.

FIG. 72A shows the result of Example Sample and FIG. 72B shows the result of Comparative Sample 1. In Comparative Sample 1, a weak symmetric signal was detected. In contrast, in Example Sample, a strong asymmetrical signal was detected. There is a high possibility that the asymmetrical signal detected in Example Sample indicates a peroxide radical of the silicon oxide.

FIGS. 73A and 73B show cross-sectional images of Example Sample and Comparative Sample 1, respectively, observed with a scanning transmission electron microscope (STEM). As the STEM, Ultra-thin Film Evaluation System HD-2300 manufactured by Hitachi High-Technologies Corporation was used. FIGS. 73A and 73B show that a difference between Example Sample and Comparative Sample 1 was hardly observed by the STEM. In addition, it was also found that a void was not formed by addition of fluorine.

According to this example, it was found that excess oxygen is formed in a silicon oxide by addition of fluorine, that excess oxygen exists as a peroxide radical in the silicon oxide, and that a difference between a silicon oxide to which fluorine is added and a silicon oxide to which fluorine is not added is hardly observed by a STEM.

EXPLANATION OF REFERENCE

200: imaging device, 201: switch, 202: switch, 203: switch, 210: pixel portion, 211: pixel, 212: subpixel, 212B: subpixel, 212G: subpixel, 212R: subpixel, 220: photoelectric conversion element, 230: pixel circuit, 231: wiring, 247: wiring, 248: wiring, 249: wiring, 250: wiring, 253: wiring, 254: filter, 254B: filter, 254G: filter, 254R: filter, 255: lens, 256: light, 257: wiring, 260: peripheral circuit, 270: peripheral circuit, 280: peripheral circuit, 290: peripheral circuit, 291: light source, 300: silicon substrate, 310: layer, 320: layer, 330: layer, 340: layer, 351: transistor, 352: transistor, 353: transistor, 360: photodiode, 361: anode, 363: low-resistance region, 370: plug, 371: wiring, 372: wiring, 373: wiring, 380: insulator, 400: substrate, 401: insulator, 402: insulator, 404: conductor, 406: semiconductor, 406 a: semiconductor, 406 b: semiconductor, 406 c: semiconductor, 412: insulator, 413: conductor, 416 a: conductor, 416 b: conductor, 422: insulator, 434: conductor, 436 c: semiconductor, 442: insulator, 450: semiconductor substrate, 452: insulator, 454: conductor, 456: region, 460: region, 462: insulator, 464: insulator, 466: insulator, 468: insulator, 472 a: region, 472 b: region, 474 a: conductor, 474 b: conductor, 474 c: conductor, 476 a: conductor, 476 b: conductor, 478 a: conductor, 478 b: conductor, 478 c: conductor, 480 a: conductor, 480 b: conductor, 480 c: conductor, 490: insulator, 492: insulator, 494: insulator, 496 a: conductor, 496 b: conductor, 496 c: conductor, 496 d: conductor, 498 a: conductor, 498 b: conductor, 498 c: conductor, 498 d: conductor, 500: substrate, 502: insulator, 503: insulator, 504: conductor, 506 a: semiconductor, 506 b: semiconductor, 506 c: semiconductor, 511: insulator, 512: insulator, 513: conductor, 514: conductor, 516: conductor, 516 a: conductor, 516 b: conductor, 522: insulator, 534: conductor, 536 a: semiconductor, 536 b: semiconductor, 536 c: semiconductor, 542: insulator, 700: substrate, 704 a: conductor, 704 b: conductor, 706: semiconductor, 706 a: semiconductor, 706 b: semiconductor, 712 a: insulator, 712 b: insulator, 714 a: conductor, 714 b: conductor, 716 a: conductor, 716 b: conductor, 718 a: insulator, 718 b: insulator, 718 c: insulator, 719: light-emitting element, 720: insulator, 721: insulator, 731: terminal, 732: FPC, 733 a: wiring, 734: sealing material, 735: driver circuit, 736: driver circuit, 737: pixel, 741: transistor, 742: capacitor, 743: switching element, 744: signal line, 750: substrate, 751: transistor, 752: capacitor, 753: liquid crystal element, 754: scan line, 755: signal line, 781: conductor, 782: light-emitting layer, 783: conductor, 784: partition wall, 791: conductor, 792: insulator, 793: liquid crystal layer, 794: insulator, 795: spacer, 796: conductor, 797: substrate, 901: housing, 902: housing, 903: display portion, 904: display portion, 905: microphone, 906: speaker, 907: operation key, 908: stylus, 911: housing, 912: housing, 913: display portion, 914: display portion, 915: joint, 916: operation key, 921: housing, 922: display portion, 923: keyboard, 924: pointing device, 931: housing, 932: refrigerator door, 933: freezer door, 941: housing, 942: housing, 943: display portion, 944: operation key, 945: lens, 946: joint, 951: car body, 952: wheel, 953: dashboard, 954: light, 1189: ROM interface, 1190: substrate, 1191: ALU, 1192: ALU controller, 1193: instruction decoder, 1194: interrupt controller, 1195: timing controller, 1196: register, 1197: register controller, 1198: bus interface, 1199: ROM, 1200: memory element, 1201: circuit, 1202: circuit, 1203: switch, 1204: switch, 1206: logic element, 1207: capacitor, 1208: capacitor, 1209: transistor, 1210: transistor, 1213: transistor, 1214: transistor, 1220: circuit, 2100: transistor, 2200: transistor, 3001: wiring, 3002: wiring, 3003: wiring, 3004: wiring, 3005: wiring, 3200: transistor, 3300: transistor, 3400: capacitor, 5100: pellet, 5100 a: pellet, 5100 b: pellet, 5101: ion, 5102: zinc oxide layer, 5103: particle, 5105 a: pellet, 5105 a 1: region, 5105 a 2: pellet, 5105 b: pellet, 5105 c: pellet, 5105 d: pellet, 5105 d 1: region, 5105 e: pellet, 5120: substrate, 5130: target, 5161: region

This application is based on Japanese Patent Application serial no. 2014-213910 filed with Japan Patent Office on Oct. 20, 2014 and Japanese Patent Application serial no. 2014-213913 filed with Japan Patent Office on Oct. 20, 2014, the entire contents of which are hereby incorporated by reference. 

1. A semiconductor device comprising: a first insulator; a second insulator; a conductor; and a semiconductor between the first insulator and the second insulator, wherein the second insulator is between the semiconductor and the conductor, wherein the first insulator includes fluorine and hydrogen, and wherein a fluorine concentration of the first insulator is higher than a hydrogen concentration of the first insulator.
 2. The semiconductor device according to claim 1, wherein the semiconductor is over the first insulator, and wherein the conductor is over the semiconductor.
 3. The semiconductor device according to claim 1, wherein the semiconductor is over the conductor, and wherein the first insulator is over the semiconductor.
 4. The semiconductor device according to claim 1, wherein the first insulator includes oxygen and silicon.
 5. The semiconductor device according to claim 4, wherein the second insulator includes fluorine.
 6. The semiconductor device according to claim 1, wherein the semiconductor includes a first semiconductor and a second semiconductor, and wherein the second semiconductor has a larger electron affinity than the first semiconductor.
 7. The semiconductor device according to claim 6, wherein the second semiconductor has a larger energy gap than the first semiconductor.
 8. The semiconductor device according to claim 1, wherein the semiconductor includes indium, zinc, oxygen and at least any one of aluminum, gallium, yttrium, and tin.
 9. A module comprising: the semiconductor device according to claim 1; and a printed board.
 10. An electronic device comprising: the semiconductor device according to claim 1 or the module according to claim 9; and at least one of a speaker, an operation key, and a battery.
 11. A semiconductor device comprising: a conductor; a first insulator; a second insulator; and a semiconductor between the first insulator and the second insulator, wherein the second insulator is between the conductor and the semiconductor, wherein the second insulator includes fluorine and hydrogen, and wherein a fluorine concentration of the second insulator is higher than a hydrogen concentration of the second insulator.
 12. The semiconductor device according to claim 11, wherein the semiconductor is over the first insulator, and wherein the conductor is over the semiconductor.
 13. The semiconductor device according to claim 11, wherein the semiconductor is over the conductor, and wherein the first insulator is over the semiconductor.
 14. The semiconductor device according to claim 11, wherein the first insulator includes oxygen and silicon.
 15. The semiconductor device according to claim 11, wherein the first insulator includes fluorine.
 16. The semiconductor device according to claim 11, wherein the semiconductor includes a first semiconductor and a second semiconductor, and wherein the second semiconductor has a larger electron affinity than the first semiconductor.
 17. The semiconductor device according to claim 16, wherein the second semiconductor has a larger energy gap than the first semiconductor.
 18. The semiconductor device according to claim 11, wherein the semiconductor includes indium, zinc, oxygen and at least any one of aluminum, gallium, yttrium, and tin.
 19. A module comprising: the semiconductor device according to claim 11; and a printed board.
 20. An electronic device comprising: the semiconductor device according to claim 11 or the module according to claim 19; and at least one of a speaker, an operation key, and a battery.
 21. A method of manufacturing a semiconductor device, comprising the steps of: forming a conductor; forming a first insulator over the conductor; forming a semiconductor over the conductor with the first insulator positioned therebetween; forming a second insulator over the semiconductor; forming a third insulator over the second insulator; and adding fluorine to the second insulator through the third insulator.
 22. The method of manufacturing a semiconductor device, according to claim 21, wherein the second insulator includes oxygen and silicon.
 23. The method of manufacturing a semiconductor device, according to claim 21, wherein the third insulator includes nitrogen and silicon.
 24. The method of manufacturing a semiconductor device, according to claim 21, wherein the semiconductor includes a first semiconductor and a second semiconductor, and wherein the second semiconductor has a larger electron affinity than the first semiconductor.
 25. The method of manufacturing a semiconductor device, according to claim 24, wherein the second semiconductor has a larger energy gap than the first semiconductor.
 26. The method of manufacturing a semiconductor device, according to claim 21, wherein the semiconductor includes indium, zinc, oxygen and at least any one of aluminum, gallium, yttrium, and tin.
 27. A method of manufacturing a semiconductor device, comprising the steps of: forming a semiconductor; forming a first insulator over the semiconductor; forming a second insulator over the first insulator; adding fluorine to the first insulator through the second insulator; and forming a conductor over the semiconductor with the first insulator and the second insulator positioned therebetween.
 28. The method of manufacturing a semiconductor device, according to claim 27, wherein the first insulator includes oxygen and silicon.
 29. The method of manufacturing a semiconductor device, according to claim 27, wherein the second insulator includes nitrogen and silicon.
 30. The method of manufacturing a semiconductor device, according to claim 27, wherein the semiconductor includes a first semiconductor and a second semiconductor, and wherein the second semiconductor has a larger electron affinity than the first semiconductor.
 31. The method of manufacturing a semiconductor device, according to claim 30, wherein the second semiconductor has a larger energy gap than the first semiconductor.
 32. The method of manufacturing a semiconductor device, according to claim 27, wherein the semiconductor includes indium, zinc, oxygen and at least any one of aluminum, gallium, yttrium, and tin.
 33. A method of manufacturing a semiconductor device, comprising the steps of: forming a first insulator; forming a second insulator over the first insulator; adding fluorine to the first insulator through the second insulator; forming a semiconductor; forming a third insulator over the semiconductor; and forming a first conductor over the semiconductor with the third insulator positioned therebetween.
 34. The method of manufacturing a semiconductor device, according to claim 33, wherein the first insulator includes oxygen and silicon.
 35. The method of manufacturing a semiconductor device, according to claim 33, wherein the second insulator includes nitrogen and silicon.
 36. The method of manufacturing a semiconductor device, according to claim 33, further comprising the steps of: forming a fourth insulator over the third insulator; adding fluorine to the third insulator through the fourth insulator; and forming a second conductor over the semiconductor with the third insulator and the fourth insulator positioned therebetween.
 37. The method of manufacturing a semiconductor device, according to claim 36, wherein the third insulator includes oxygen and silicon.
 38. The method of manufacturing a semiconductor device, according to claim 36, wherein the second insulator includes nitrogen and silicon.
 39. The method of manufacturing a semiconductor device, according to claim 33, wherein the semiconductor includes a first semiconductor and a second semiconductor, and wherein the second semiconductor has a larger electron affinity than the first semiconductor.
 40. The method of manufacturing a semiconductor device, according to claim 39, wherein the second semiconductor has a larger energy gap than the first semiconductor.
 41. The method of manufacturing a semiconductor device, according to claim 33, wherein the semiconductor includes indium, zinc, oxygen and at least any one of aluminum, gallium, yttrium, and tin. 